臺灣博碩士論文加值系統

柑橘加工業每年產生大量副產物，用作動物飼料或直接丟棄而導致嚴重的環境問題。Citrus reticulata，中文名為椪柑，含有多種有益於人體健康的植化素，如多酚及類黃酮等，為了妥善利用椪柑副產物，本研究擬用真空微波乾燥 (microwave vacuum drying, MVD) 處理，結合超聲輔助萃取並以不同濃度之乙醇進行萃取，測定椪柑果皮總酚含量 (total phenolic contents, TPC)、總黃酮含量 (total flavonoid contents, TFC)、總抗壞血酸含量 (total ascorbic acid contents, TAAC)、以 HPLC-PDA 進行黃烷酮含量分析及抗氧化活性。而後將醇不溶性殘餘物使用鹽酸、硫酸、檸檬酸和水萃取果膠，分析產率、半乳醣醛酸 (galacturonic acid, GalA)、酯化度 (degree of esterification, DE)、起泡性、保水力 (water holding capacity, WHC)、保油力 (oil holding capacity, OHC)、色度、掃描式電子顯微鏡 (scanning electron microscopy, SEM)、TPC、TFC 及抗氧化活性，最後將萃取完果膠之剩餘物進行總膳食纖維分析 (total dietary fiber contents, TDF)，評估未來開發功能性食品的潛力，以增加椪柑副產物之價值。結果表明，TPC 及 TFC 隨著乙醇濃度升高而上升，尤其是 75% 的乙醇萃取最高 (17.48 mg GAE/g DW、2.96 mg QE/g DW)，且呈現出最高的抗氧化活性，但 95% 的乙醇萃取效果則無 75% 萃取來得顯著。由於水溶性及醇溶性之原因，TAAC 以水萃取最佳 (13.07 mg VitC/100g DW)，而 HPLC-PDA 分析黃烷酮以 95% 乙醇萃取液總含量最高，分別為 hesperidin 含量最高，其次為 naringin、neohesperidin 及 naringenin。鹽酸萃取果膠 (hydrochloric acid extraction pectin, HEP) 之 WHC 及 OHC 最高 (9.12 g H2O/g DW 及 0.51 g oil/g DW)；硫酸萃取果膠 (sulfuric acid extraction pectin, SEP) 的泡沫體積最高 (0.18-0.30 mL)，作為起泡劑方面具有潛力；檸檬酸萃取果膠 (citric acid extraction pectin, CEP) 之產率最高 (19.57%)，而雖然水萃取果膠 (water extraction pectin, WEP) 產率最低 (4.02%)，但其亮度最高 (L* = 83.24)，且偏向綠黃色。四種不同溶劑萃取果膠之 GalA 為 61.33-75.81%，DE 為 75.66-76.44%，皆為高甲氧基果膠。在 SEM 中由側面圖像可看出果膠皆為層層堆疊且無孔洞。由表面圖像可看出，除 SEP 以外，其餘表面結構皆光滑，具有良好的抗變形凝膠能力。果膠之 TPC、TFC 及抗氧化能力顯著低於果渣，表明在前處理部分之 75% 乙醇可有效將雜質去除，從而萃取出高甲氧基果膠。經 MVD 後之果渣 TDF 為 25.83%，萃取果膠後之剩餘物 TDF 為 13.39-17.02%，可能是由於可溶性膳食纖維已被萃取出，故推論此部分為不可溶性膳食纖維。綜上所述，椪柑副產物未來具有開發功能性食品和成為天然抗氧化劑的潛力，且其果膠能用作膠凝劑、增稠劑和穩定劑使用，而萃取完果膠之剩餘物可用作膳食補充劑或添加於冰淇淋中應用，以增加椪柑副產物之價值。

Citrus-processing industries generate 80 million tons of wastes every year, and the disposal of these wastes presents serious environmental problems. Citrus reticulata, called Ponkan, which contains a number of nutrients beneficial to human health. In this study, microwave vacuum drying (MVD) was combined with ultrasound-assisted extraction to compare with different ethanol volume of extract and to evaluate total phenolic contents (TPC), total flavonoid content (TFC), total ascorbic acid content (TAAC), using HPLC-PDA to analysis flavanone contents, and antioxidant activity of Ponkan peels. Then, the ethanol insoluble residue extracts the pectin with four different solvents, evaluating galacturonic acid (GalA) contents, degree of esterification (DE), foam volume, water holding capacity (WHC), oil holding capacity (OHC), color variation, scanning electron microscopy (SEM), TPC, TFC, and antioxidant activity. Lastly, the residue after the pectin extract was analyzed for total dietary fiber contents (TDF). Not only to evaluate the potential of developing functional food in the future, but also to increase the value of ponkan by-products and for further processing as a reference. Experimental results showed the TPC and TFC increases with ethanol volume. 75% ethanol extraction showed significant advantages in increasing the TPC (17.48 mg GAE/g DW) and TFC (2.96 mg QE/g DW) of Ponkan extracts, as well as presented the highest antioxidant activity. However, 95% ethanol extraction wasn’t as effective as 75% extraction. TAAC increased with the water content. Water extraction had the highest content (13.07 mg VitC/100g DW), and 95% ethanol extraction had the lowest content (9.76 mg VitC/100g DW). The hesperidin contents analyzed by HPLC-PDA was 102.95-622.57 mg/100 g DW, which is the highest among flavanone. The lowest one was naringenin (0.72-6.69 mg/100 g DW). The WHC and OHC of hydrochloric acid extraction pectin (HEP) were the hightest (9.12 g H2O/g DW and 0.51 g oil/g DW). The sulfuric acid extraction pectin (SEP) had the highest foam volume (0.18-0.30 mL). The highest yield of pectin was retained by using citric acid extraction (CEP) (19.57%). The water extraction pectin (WEP) showed light tan. The DEs of four different solvents were 75.66-76.44%, which are high-methoxyl pectin. The SEM figures showed that pectin with four different solvents extraction present a dense and smooth layered structure. The tight network structure provided pectin with a better deformation resistance. The TPC, TFC and antioxidant capacity of pectin are significantly lower than the peels, indicating that 75% ethanol in the pre-treatment part can effectively remove polyphenols, flavonoids, etc., thereby extracting high-methoxyl pectin. The TDF contents of MVD Ponkan by-products were 25.83%. The residue after Citrus reticulata pectin extract with different solvents TDF contents were 13.39-17.02%. the flavor industry. In conclusion, Ponkan by-products has the potential for future development of functional foods and supplements. Its pectin has the potential for gelling agent, thickening agent, and stabilizer. The residue after Citrus reticulata pectin extract can be used as dietary supplement or added to ice cream to increase the value of ponkan by-products.

壹、前言 1
貳、文獻回顧 2
一、柑橘資料 2
1.1 柑橘介紹 2
1.2 柑橘之分類 2
1.3 臺灣柑橘屬水果種植狀況 5
1.4 柑橘屬水果副產物之介紹 5
二、柑橘中的植化素 7
2.1 類黃酮 7
2.2 酚酸 9
2.3 膳食纖維 9
2.4 精油 12
2.5 類胡蘿蔔素 13
2.6 抗壞血酸 14
三、乾燥方法 15
3.1 真空微波乾燥 15
3.2 冷凍乾燥 15
3.3 熱風乾燥 15
3.4 紅外線輻射乾燥 16
3.5 滲透乾燥 16
四、萃取植化素方法 17
4.1 抗氧化成分 17
4.2. 果膠 18
參、實驗流程 20
一、植化素含量及抗氧化能力測定 20
二、果膠的萃取及分析 21
肆、實驗材料與方法 22
一、實驗材料 22
1.1 樣品 22
1.2 實驗藥品與試劑 22
1.3 標準品 23
二、實驗方法 23
2.1 椪柑副產物樣品之處理 23
2.2 乾燥產率 24
2.3 水活性測定 24
2.4 一般成分分析 24
2.5. 類黃酮化合物萃取 24
2.6. 植化素含量之分析 24
2.7. 果膠特性分析 26
2.8 抗氧化能力分析 29
2.9 總膳食纖維含量 30
2.10 統計分析 30
伍、結果與討論 31
一、椪柑副產物之乾燥結果 31
二、椪柑副產物之一般成分分析 31
三、萃取溶劑對椪柑副產物之植化素含量分析結果 31
3.1 總酚含量之影響 31
3.2 總類黃酮含量之影響 32
3.3 總抗壞血酸含量之影響 32
3.4 以 HPLC-PDA 分析椪柑副產物萃取液之黃烷酮含量 32
四、萃取溶劑對椪柑副產物之抗氧化能力 33
4.1 ABTS 自由基清除能力 34
4.2 DPPH 自由基清除能力之影響 34
4.3 FRAP 鐵還原抗氧化能力之影響 34
五、萃取條件對果膠產率之影響 35
六、萃取溶劑對果膠之物化特性分析結果 36
6.1 純度 36
6.2 酯化性 36
6.3 起泡性 37
6.4 保水力 37
6.5 保油力 37
6.6 色度分析 38
6.7 掃描式電子顯微鏡 38
七、萃取溶劑對果膠之植化素含量分析結果 38
7.1 總酚含量之影響 38
7.2 總類黃酮含量之影響 38
八、萃取溶劑對果膠之抗氧化能力 39
8.1 DPPH 自由基清除能力之影響 39
8.2 FRAP 鐵還原抗氧化能力之影響 39
九、椪柑副產物之總膳食纖維含量 39
陸、結論 41
柒、未來發展 42
捌、參考資料 43
玖、圖表 61
拾、附錄 87

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