臺灣博碩士論文加值系統

澱粉廣泛應用於食品及非食品工業中，作為增稠劑、穩定劑、凝膠劑等。然而，天然澱粉在工業應用上容易出現老化回凝、收縮離水、抗熱性等性質。現今已經使用各種方法，包括化學、物理、酵素和遺傳修飾來製備具有特定功用的修飾澱粉，以滿足各種工業的需求及應用。本篇研究採用化學的方法製備羥丙基化、交聯化和雙重修飾樹薯澱粉，並探討其最適實驗條件及功能性質。
結果顯示，修飾的最適製備條件分別為羥丙基化澱粉(9HS)為添加量9%環氧丙烷試劑於40 ℃反應24小時；羥丙基化-交聯雙重修飾澱粉(9HSCL1)為添加STMP/STPP (99/1)濃度為0.25 %於45 ℃反應1小時；交聯-羥丙基化雙重修飾澱粉(30CL9HS)為添加量9 %環氧丙烷試劑於40 ℃反應24小時。從快速粘度分析儀(RVA)分析結果得知，經過修飾後的澱粉與天然澱粉相較下其最終黏度上升，尖峰時間及糊化溫度則顯著下降，觀察到雙重修飾的順序會影響黏度特性，尤其是在30CL9HS能觀察到。當添加環氧丙烷濃度越高，其羥丙基團及莫耳取代會隨著升高，經過修飾後的澱粉其羥丙基團、莫耳取代度及磷酸根含量皆在法規的限量標準之中。所有三種修飾和天然樹薯澱粉的功能特性，包括透光率、直鏈澱粉含量、凝膠延展性，凍融穩定性(FTS)、溶解度和膨脹力，結果顯示9HS、9HSCL1及 30L9HS與天然澱粉(UNS)相較下，其透光度、直鏈澱粉含量皆下降，但有較佳的凝膠延展性。9HSCL1及30CL9H離水率最低，代表在低溫下具有良好的安定性。另外，天然及修飾樹薯澱粉其溶解度及膨潤力結果顯示，膨脹力和溶解度均隨溫度的升高而增加。傅立葉紅外線光譜(FTIR)顯示雙重修飾澱粉的醚基及酯基分別在1050-1200 cm -1及995-1050 cm -1吸收峰之間具有顯著的吸收峰。示差掃描熱分析(DSC)結果顯示，經過修飾澱粉的澱粉，其糊化起始溫度(TO)、最終糊化溫度(TC)、糊化尖峰溫度(TP)及熱焓值ΔH皆下降。X-ray顯示，天然樹薯介於A-type及B-type之間屬於C-type，經過修飾後的澱粉仍維持C-type，表示羥丙基化及交聯化主要是發生在結構的不定形區域。另外，掃描式電子顯微鏡（SEM）觀察顆粒外觀天然和修飾澱粉之間有些微的變化。感官品評結果顯示，天然澱粉經修飾後其特性有顯著改善。透過冷藏及DSC分析各種澱粉的老化程度結果顯示，發現完全糊化之天然澱粉在4 ℃冷藏30分鐘後快速老化高達57%，而完全糊化之交聯-羥丙基雙重修飾澱粉及市售修飾澱粉在4 ℃冷藏儲存第三天才出現老化現象，充分證明澱粉經過交聯-羥丙基化雙重修飾後，確實可以延緩澱粉的老化。本篇研究所製備的交聯-羥丙基化雙重修飾樹薯澱粉其功能性質與市售修飾澱粉相近，其抗老化及增稠的特性，在食品加工工業上非常有潛力。

Starch is widely application in food and non-food industry as thickener, stabilizer, gelling agent. However, the properties of native starch are easy to retrogradation, syseresis, and thermal resistance in industrial application. Now, including chemical, physical, enzymatic, and genetic modifications have been used to prepare modified starches with desirable functionalities to meet various industrial applications. The objective of this study was optimum process condition for production of dually modified starches from cassava starches by hydroxypropylated and STMP-STPP cross-linking.
The results show that the optimum process condition of hydroxypropylated starch (9HS) was added 9 % propylene oxide, reaction at 40℃ for 24 h, hydroxypropylated cross-linkined dually modified starch (9HSCL1) was added STMP / STPP (99/1), 0.25 %, reaction at 45℃ for 1 h, cross-linkined hydroxypropylated dually modified starch (30CL9HS) was added 9% propylene oxide, reaction at 40℃ for 24 h. The analysis of Rapid Viscosity Analyzer (RVA) results show that the Final vise of modified starch were higher than native cassava starch, peak time and pasting temperature were significant decrease. The sequence in which the dual modifications were observed also affected the properties of starch, especially in 30CL9HS. When the amount of added propylene oxide increased, the hydroxypropyl group and MS with corresponding increases. Hydroxypropyl group, MS, and phosphate content of the modified starch were within the limit allowed of the code. The functional characteristics, including light transmittance, amylose content, gel consistency, freeze-thaw stability (FTS), solubility, and swelling power, of three modified and native cassava starches demonstrated that 9HS, 9HSCL1, and 30CL9HS had the lower light transmittance and amylose content, but had the better gel consistency than native cassava starches. The freeze-thaw stability of 9HSCL1 and 30CL9HS had the lowest water loss, which is stable to low temperatures. In addition, the date of native and modified cassava starch showed that the solubility and swelling power of all the starch samples increased with the increase of temperature. Results from Fourier-transform infrared spectroscopy (FTIR) show that dual modified starch of ether bond and ester bond had significant absorption peak at 1050-1200 cm-1 and 995-1050 cm-1, respectively. The data of differential scanning calorimeters (DSC) showed that the initial onset temperature (TO), the conclusion temperature (TC), the peak temperature (TP) and the transition enthalpy ΔH of modified starches were all lowered. The date of X-ray showed that native cassava starch between the A-type and B-type belong to C-type. All of the modified starches were keet C-type. Both of hydroxypropyl and cross-linked were occur in the amorphous regions of starch granule. Moreover, the scanning electron microscopic (SEM) photographs showed there were only slight changed between the native and modified starches. The results of sensory evaluation showed that the modification of native cassava starch significantly improved it characteristics. The results of retrogradation of various starches by refrigeration and subsequent DSC analysis showed that the completely gelatinized native cassava starch retrogradated rapidly to 57 % (DR) after being storaged at 4°C for 30 minutes, while the completely gelatinized dually modified starch and the commercially modified starch retrogradated until the third day after being storage at 4°C. It is fully proved that the retrogradation of starch can be delayed by dual modification. The dually modified cassava starch prepared in this study has exhibited similar functional and physicochemical properties to commercial modified starch. Owning to its anti-retrogradation and thickening properties is promising in the food processing industry.

中文摘要 I
英文摘要 III
目錄 VI
表目錄 X
圖目錄 XI
壹、前言 1
貳、文獻回顧2
一、澱粉(Starch)2
(一)樹薯澱粉(Cassava Starch)6
二、澱粉顆粒結構9
三、澱粉性質14
(一)澱粉糊化(Gelatinization)14
(二)澱粉離水(Syneresis)14
(三)澱粉老化 (Retrogradation or staling)14
四、修飾澱粉((Modified Starches)17
(一)醚化澱粉(Etherified Starch)22
(二)交聯澱粉(Cross-linking starch)25
參、材料與方法29
一、實驗架構29
二、實驗材料及儀器設備30
三、實驗方法30
(一)基本成分分析30
1、水分(Water content)30
2、灰分(Ash)31
3、粗脂肪 (Crude fat)31
4、粗蛋白(Crude protein)32
5、直鏈澱粉含量之測定32
6、磷酸根含量之測定33
(二)修飾澱粉之製備34
1、羥丙基化樹薯澱粉之製備34
2、交聯樹薯澱粉之製備34
3、雙重化學修飾澱粉之製備35
(三)快速黏度分析(Rapid Visco Analysis)35
(四)理化特性36
1、羥丙基團及莫耳(Molar substitution, MS)取代程度之測定36
2、澱粉糊透光度率之測定(Transmittance)37
3、凝膠延展性( Gel consistency)37
4、冷凍-解凍循環穩定度之測定(Freeze-thaw stability)37
5、溶解度(Solubility)及膨潤力(Swelling power)38
6、X-ray繞射分析(X-ray Diffraction Analysis)39
7、傅立葉紅外線光譜(Fourier-transform infrared spectroscopy)39
8、示差掃描熱分析(Differential Scanning Calorimeters)39
9、掃描式電子顯微鏡之觀察(Scanning Electron Microscopic)40
(五)感官品評(Sensory evaluation)40
(六)老化程度測定(Determination of degree of retrogradation)41
(七)統計分析42
肆、結果與討論43
一、基本成分分析43
二、羥丙基化交聯化雙重修飾樹薯澱粉其最適生產條件之探討45
三、理化特性51
(一)羥丙基團及莫耳(Molar substitution, MS)取代程度之測定51
(二)澱粉糊透光率、直鏈澱粉及凝膠延展性含量分析55
(三)冷凍-解凍安定性試驗(Freeze-thaw stability)59
(四)溶解度(Solubility)及膨潤力(Swelling power)64
(五)X-ray繞射圖譜68
(六)傅立葉紅外線光譜分析(Fourier-transform infrared spectroscopy)71
四、示差掃描熱分析(Differential Scanning Calorimeters)76
五、掃描式電子顯微鏡觀察(Scanning Electron Microscopic)79
六、感官品評(Sensory Evaluation)83
七、老化程度測定(Determination of degree of retrogradation)86
伍、結論 95
陸、參考文獻98
附錄117

表目錄
表一、不同植物來源之澱粉顆粒形態及大小4
表二、不同植物來源之澱粉顆粒特性5
表三、樹薯之基本成分分析結果一覽表8
表四、修飾澱粉之種類及特性20
表五、台灣准用之食用修飾澱粉品項21
表六、天然樹薯澱粉基本成分分析結果一覽表44
表七、不同濃度環氧丙烷對天然樹薯澱粉進行羥丙基化其熱糊特性之影響48
表八、不同反應時間對天然及羥丙基化樹薯澱粉進行交聯化其熱糊特性之影響49
表九、不同環氧丙烷濃度對天然及交聯樹薯澱粉進行羥丙基化其熱糊特性之影響50
表十、天然及修飾樹薯澱粉之羥丙基團、莫耳取代度及磷酸根含量一覽表54
表十一、天然和雙重修飾樹薯澱粉糊其透光率、直鏈澱粉及凝膠延展性含量一覽表58
表十二、天然和雙重修飾樹薯澱粉其熱特性分析一覽表78
表十三、天然、交聯羥丙基化及市售修飾樹薯澱粉所製之粉圓其感官品評與冷藏貯存之關係85
表十四、天然和雙重修飾樹薯澱粉其老化熱特性分析一覽表88

圖目錄
圖一、澱粉顆粒結構11
圖二、直鏈澱粉(A)及支鏈澱粉(B)之結構12
圖三、A、B與V型澱粉之X-RAY繞射圖譜13
圖四、快速黏度分析(RAPID VISCO ANALYSER, RVA)曲線圖16
圖五、環氧丙烷與澱粉反應機制圖24
圖六、交鏈試劑與澱粉反應機制28
圖七、不同濃度環氧丙烷對樹薯澱粉莫耳取代度的影響53
圖八、天然及羥丙基化樹薯澱粉膠體於不同次數之冷凍-解凍循環下之離水率62
圖九、天然及雙重修飾樹薯澱粉膠體於不同次數之冷凍-解凍循環下之離水率63
圖十、溫度對天然及雙重修飾樹薯澱粉其溶解度之影響66
圖十一、溫度對天然及雙重修飾樹薯澱粉其膨潤力之影響67
圖十二、天然及雙重修飾樹薯澱粉之X-射線繞射圖譜70
圖十三、天然和修飾樹薯澱粉其傅立葉轉換紅外線光譜圖73
圖十四、天然和雙重修飾樹薯澱粉其傅立葉轉換紅外線光譜圖74
圖十五、天然和雙重修飾樹薯澱粉其傅里葉轉換紅外線光譜圖75
圖十六、天然及羥丙基化樹薯澱粉其掃描式電子顯微鏡圖81
圖十七、天然及雙重修飾樹薯澱粉其掃描式電子顯微鏡圖82
圖十八、儲存天數對天然及雙重修飾樹薯澱粉其老化度之影響89
圖十九、儲存時間對天然樹薯澱粉其老化度之影響90
圖二十、儲存時間對天然樹薯澱粉其老化之熱分析圖91
圖二十一、儲存天數對天然樹薯澱粉其老化之熱分析圖92
圖二十二、儲存天數對雙重修飾樹薯澱粉其老化之熱分析圖93
圖二十三、儲存天數對市售修飾樹薯澱粉其老化之熱分析圖94

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