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研究生:任品靜
研究生(外文):JEN, PIN-CHING
論文名稱:以柑橘皮製備生物吸附劑應用於食米中重金屬去除之研究
論文名稱(外文):Preparation of biosorbents from citrus peels for the removal of heavy metals from rice
指導教授:陳志瑋陳志瑋引用關係
指導教授(外文):CHEN, CHIH-WEI
口試委員:張基郁梁哲豪
口試委員(外文):CHANG, CHI-YUELIANG, JER-HOUR
口試日期:2023-05-31
學位類別:碩士
校院名稱:長榮大學
系所名稱:安全衛生科學碩士學位學程
學門:醫藥衛生學門
學類:公共衛生學類
論文種類:學術論文
論文出版年:2023
畢業學年度:111
語文別:中文
論文頁數:186
中文關鍵詞:柑橘皮生物吸附劑稻米重金屬吸附抗氧化能力生物活性成分
外文關鍵詞:citrus biosorbentsriceheavy metaladsorptionantioxidant activitybiological activity ingredient
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柑橘是全世界最熱門的水果之一,因此全球每年會產生大量柑橘皮,其果皮有很好經濟價值,但大多數情況下,果皮被作為廢棄物丟棄。在工業進步及城市化快速發展之下,土壤和農產品重金屬污染問題是當前國內外的研究熱點,其中以稻米中重金屬污染特為重要,世界上將近一半的人口都食用稻米,這對消費者構成了食品安全的威脅,為了減少人類對鎘或其他有毒金屬的接觸,特別是通過攝入食米和食米產品,應考慮改變某些植物收穫後的做法,進一步降低重金屬危害,因此本研究係利用日常生活中常見的廢棄果皮,以天然或低成本的簡單加工萃取方式製備不同萃取物移除標的物(食米)中有毒金屬(如鎘等金屬)及提升其生物活性成分,為開發具有吸附重金屬能力同時又具可食性之綠色健康材料,使果皮廢棄物再利用產生循環經濟。

根據研究結果發現,以柑橘皮(Citrus peel, CP)作為不同製備法(water (CPW-ext), ethanol (CPE-ext), cellulase (CPC-ext), pectinase (CPP-ext), cellulase and pectinase (CPC+P-ext))所得的生物吸附劑,在生物活性成分及抗氧化活性方面,在生物吸附劑濃度1 mg/mL下,其類黃酮及花青素含量較高的是CPE-ext,總多酚及總多醣含量較高的分別是酵素處理生物吸附劑(CPC-ext、CPP-ext及CPC+P-ext)及CPW-ext,其中以CPE-ext對螯合亞鐵離子能力、抑制α-澱粉酶活性、清除DPPH自由基及羥基自由基的效果較佳,抑制α-葡萄糖苷酶及脂解酶活性能力最強的是酵素處理生物吸附劑(CPC-ext、CPP-ext及CPC+P-ext)及CPW-ext。在吸附重金屬能力方面,最適條件試驗所得之最適浸泡時間及濃度分別為1小時浸泡及5 mg/mL生物吸附劑濃度其吸附重金屬效果較佳,接著再將最適浸泡條件套用至不同製備法所得生物吸附劑浸泡不同品種的稻米,與原始生米作為陽性對照組,生物吸附劑浸泡生米所移除重金屬的效果比水浸泡較佳,其中移除砷及鎘金屬較好的生物吸附劑是CPE-ext,移除銅效果較好的生物吸附劑是CPW-ext,在水洗及烹煮時,黑米、白米及糙米中砷及重金屬皆有顯著性下降,最後,本研究證實添加柑橘生物吸附劑的效益,以及水洗、浸泡及烹調對重金屬的移除具有顯著性效果。

Citrus is a prevalent fruit around the world, resulting in the production of numerous citrus peels annually. Unfortunately, these peels are typically discarded as waste despite their potential economic value. With the ongoing issue of heavy metal pollution in soil and agricultural products, particularly rice, a staple food for almost half of the world's population, reducing the threat to consumers is vital. To address this, post-harvest practices should be implemented to lessen human exposure to toxic metals such as cadmium. This study focuses on utilizing discarded fruit peels through natural or low-cost processing and extraction methods to remove toxic metals in rice and enhance its biological activity element. This green and healthy approach enables the recycling of fruit peel waste, generating a circular economy. The research revealed that different preparation methods (water, ethanol, cellulase, pectinase, and a combination of cellulase and pectinase) resulted in biosorbents with varying bioactive ingredients and antioxidant activity. The CPE-ext preparation method had the highest flavonoid and anthocyanin content. In contrast, enzyme-treated biosorbents (CPC-ext, CPP-ext, and CPC+P-ext) and CPW-ext had higher total polyphenols and polysaccharides content. CPE-ext could chelate ferrous ions, scavenge DPPH and hydroxyl free radicals, and inhibit α-amylase activity. Enzyme-treated biosorbents (CPC-ext, CPP-ext, and CPC+P-ext) and CPW-ext had the most potent ability to inhibit α-glucosidase and lipolytic enzyme activity.

Regarding the ability to adsorb heavy metals, the optimal soaking time and biosorbent concentration were 1 hour and 5 mg/mL, respectively. The best biosorbent for removing arsenic and cadmium metals was CPE-ext, while CPW-ext had a better copper removal effect. Soaking rice in biosorbents showed a better removal of heavy metals than water soaking, and washing and cooking further decreased the arsenic and heavy metal content in black, white, and brown rice. Overall, this study highlights the effectiveness of citrus biosorbent and emphasizes the importance of washing, soaking, and cooking in removing heavy metals from rice.

誌謝 I
中文摘要 II
ABSTRACT IV
縮寫對照表 VI
目錄 VIII
表目錄 XII
圖目錄 XV
1. 緒論 1
2. 文獻探討 3
2.1. 廢棄果皮及稻米之活性成分與功效 3
2.1.1. 柑橘 6
2.1.2. 稻米 6
2.2. 酵素 7
2.2.1. 纖維素酶 7
2.2.2. 果膠酶 9
2.2.3. α-澱粉酶 10
2.2.4. α-葡萄糖苷酶 10
2.2.5. 脂解酶 11
2.3. 抗氧化與自由基 12
2.4. 酚類化合物 15
2.5. 花青素 16
2.6. 有機酸 17
2.7. 果皮吸附重金屬之機制 18
2.8. 重金屬來源與危害 21
2.9. 稻米中常見的重金屬與微量元素 24
2.9.1. 砷 (Arsenic, As) 24
2.9.2. 鎘 (Cadmium, Cd) 26
2.9.3. 鎂 (Magnesium, Mg) 27
2.9.4. 錳 (Manganese, Mn) 28
2.9.5. 鋅 (Zine, Zn) 28
2.9.6. 鐵 (Iron, Fe) 28
2.9.7. 銅 (Copper, Cu) 29
3. 研究方法 29
3.1. 樣品選擇 29
3.1.1. 稻米 29
3.1.2. 果皮 30
3.2. 材料 32
3.2.1. 試藥級藥品 32
3.2.2. 設備 34
3.3. 生物吸附劑製備 35
3.3.1. 熱水萃取 35
3.3.2. 酒精溶劑萃取 35
3.3.3. 酵素處理萃取 36
3.4. 有機酸含量測定 37
3.5. 生物活性成分測定 38
3.5.1. 總多酚含量分析 38
3.5.2. 類黃酮含量分析 38
3.5.3. 總多醣含量分析 39
3.5.4. 總花青素含量測定 40
3.6. 抗氧化成分評估 40
3.6.1. 清除DPPH自由基能力 40
3.6.2. 亞鐵離子螯合能力 (Ferrous Ion Chelating Assay) 42
3.6.3. 羥基自由基清除能力(去氧核醣測定) 43
3.7. 代謝能力評估 44
3.7.1. 抑制 α-amylase 活性評估 44
3.7.2. 抑制 α-glucosidase 活性評估 44
3.7.3. 抑制 Lipase 活性評估 45
3.8. 稻米製備 45
3.9. 重金屬分析 45
3.9.1. 最佳浸泡條件試驗-時間 46
3.9.2. 最佳浸泡條件試驗-濃度 46
3.9.3. 生物吸附劑對食米中金屬移除能力試驗 46
3.9.4. 重金屬含量測定 47
3.9.5. pH值分析 50
3.10. 統計分析 50
4. 結果與建議 51
4.1. 生物吸附劑之有機酸含量測定 51
4.2. 生物活性成分測定 54
4.2.1. 總多酚 54
4.2.2. 類黃酮 58
4.2.3. 總多醣 61
4.2.4. 總花青素 65
4.3. 抗氧化活性評估 70
4.3.1. 清除DPPH自由基能力評估 70
4.3.2. 螯合亞鐵離子測定 75
4.3.3. 羥基自由基清除能力測定(去氧核醣測定) 78
4.4. 代謝活性能力評估 83
4.4.1. 抑制α-amylase活性能力評估 83
4.4.2. 抑制α-glucosidase活性能力評估 87
4.4.3. 抑制Lipase活性能力評估 91
4.5. 生物吸附劑之金屬含量分析 95
4.6. 稻米中金屬含量分析 97
4.6.1. 不同時間浸泡影響 97
4.6.2. 不同濃度浸泡影響 100
4.6.3. pH分析 103
4.6.4. 生物吸附劑浸泡稻米對米中砷及重金屬移除的影響 105
4.6.5. 生物吸附劑浸泡稻米對米中微量元素的影響 114
4.6.6. 稻米經浸泡處理及烹煮後對米中砷及重金屬移除的影響 121
4.6.7. 稻米經浸泡處理及烹煮後在對米中微量元素的影響 127
4.7. 相關性分析 133
4.7.1. 黑米與抗氧化能力之相關性 133
4.7.2. 白米及糙米與抗氧化能力之相關性 139
5. 結論 145
6. 文獻參考 146


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