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研究生:曹碧鳳
論文名稱:蜂蜜真偽之鑑定及其品質之評估
論文名稱(外文):Studies on the adulteration identification and the quality evaluation of honey
指導教授:溫惠美溫惠美引用關係陳景川陳景川引用關係
學位類別:碩士
校院名稱:國立屏東科技大學
系所名稱:食品科學系
學門:農業科學學門
學類:食品科學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
論文頁數:120
中文關鍵詞:蜂蜜花蜜品質評估真偽鑑定
相關次數:
  • 被引用被引用:18
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中文摘要
本研究針對台灣北、中、南三地所蒐集之16件蜂農蜜樣品與屏東及台南縣市蒐集之15件市售蜂蜜樣品,進行蜂蜜真偽之鑑定與品質評估之分析。分析項目包括一般成分分析、礦物質及微量元素、醣類、pH、可滴定酸、HMF、澱粉酶活性、總生菌數、類黃酮物質、花粉總數與鑑定等。
蜂農蜜及市售蜂蜜之一般成分分析顯示:蜂農蜜水分含量約15.77~20.85%,灰分含量約0.09~0.23%,粗蛋白含量約0.24~0.55%;市售蜂蜜部分,水分含量約16.40~20.57%,灰分含量約<0.01~0.05%,粗蛋白含量約0.03~0.16%。
蜂蜜品質方面,蜂農蜜礦物質以Na,K,P與Ca含量為最高,分別為77.67~768.27ppm,64.50~335.11ppm,61.41~215.57ppm與11.08~191.18ppm。醣類部份,果糖為26.60~38.35%,葡萄糖為19.83~36.95%,蔗糖為未檢出到0.32%,麥芽糖為未檢出到4.70%,還原糖為50.74~74.66%。pH為3.73~5.06,可滴定酸為8.43~38.17meq/kg,α-amylase為64.83~118.68mg.maltose/min.g,β-amylase為24.42~354.72mg.maltose/min.g。HMF為未檢出到419.17ppm。總生菌數為0~32 CFU/g。市售蜜部份,礦物質同樣以Na,K,P與Ca含量為主,分別為36.03~198.30ppm,未檢出~340.20ppm,13.88~66.65ppm與52.71~2494.80ppm。醣類部份,果糖為15.81~44.85%,葡萄糖為15.87~33.94%,蔗糖為未檢出~23.45%,麥芽糖為未檢出~2.88%,還原糖為31.68~75.20%,pH為4.42~6.08,可滴定酸為1.01~8.51meq/kg。α-amylase為37.71~152.52 mg.maltose/min.g,β-amylase為31.11~161.37mg.maltose/min.g。HMF為49.44~195.62 ppm,總生菌為0~35CFU/g。
16件蜂農蜜中除6件之還原糖(F+G)低於60%與4件之HMF偏高外,其餘大多數樣品均符合中國國家標準甲級蜜之要求。市售蜂蜜部分,蔗糖含量有部分樣品高達8.55%,19.64%與23.45%,未達乙級蜜之要求,HMF含量則全數均未達乙級蜜之要求。
蜂蜜真偽鑑定,以毛細管區帶電泳法(CZE)進行蜂蜜類黃酮物質的定性。蜂農蜜部分有naringin,morin,myricetin,kaempferol,apigenin與galangin等6種可被鑑定出。市售蜂蜜以naringin,myricetin,apigenin,quercitrin與galangin等5種被鑑定出。
花粉總數之計算與鑑定,蜂農蜜部分,花粉含量為1560~19240pollen/g,可鑑定出23科。市售蜜部分,花粉含量為0~2670pollen/g,可鑑定出15科。兩者花粉出現之頻率均以無患子科(龍眼、荔枝)最為常見,十字花科、菊科、大戟科(血桐、白匏子)與榆科(山黃麻)等次之。以2000pollen/g為真偽界定標準,顯示市售蜂蜜之花粉含量僅13.33%達到真蜜標準,有9件樣品完全無花粉存在。
由實驗結果得知,蜂蜜真偽鑑定必須以花粉總量與種類,類黃酮,HMF與醣類多種指標共同搭配,方可得到較為客觀的評估結果。
Abstract
The objectives of this study were to identify the adulteration and to evaluate the quality of 16 honey samples collected from beekeepers of northern, middle, and southern Taiwan, and 15 commercial products which purchased from the retail stores of Pingtung and Tainan area.The analysis items included proximate analysis, mineral analysis, saccharide contents determination, pH and titratable acidity analysis, HMF contents measurement, diastase activity analysis, aerobic plate content measurement, flavonoids identification, and pollen counts and its taxonomic identification.
The proximate analysis showed moisture, ash, and crude protein contents in honey from beekeepers were 15.77~20.85%, 0.09~0.23%, and 0.24~0.55%, respectively, and of those were 16.40~20.57%, <0.01~0.05%, and 0.03~0.16% in commercial honey products. Mineral contents of Na, K, P, and Ca in honey from beekeepers were about 77.67~768.27ppm, 64.50~335.11ppm, 61.41~215.57ppm, and 11.08~191.18ppm, respectively, and of those were 36.03~198.30ppm, ND~340.20ppm, 13.88~66.65ppm, and 52.71~2494.80ppm in commercial products.
Quality evaluation included the indices of sugar contents, pH, titratable acidity, diastase activity, HMF contents, and aerobic plate contents. The results showed saccharide contents of fructose, glucose, sucrose, maltose and reducing sugar in samples from beekeepers were about 26.60~38.35%, 19.83~36.95%, ND~0.32%, ND~4.70%, and 50.74~74.66%, respectively. In commercial products, the contents of fructose, glucose, sucrose, maltose, and reducing sugar were ranged from 15.81~44.85%, 15.87~33.94%, ND~23.45%, ND~2.88%, and 31.68~75.20%. pH range of honey from beekeepers and from commercial products were from to 3.73~5.06, and from 4.42 to 6.08, respectively. Titratable acidity analysis showed 8.43~38.17meq/kg in honey from beekeepers and 1.01~8.51meq/kg in commercial products. Diastase activity tests revealed that ranged of 64.83 to 118.68mg.maltose/min.g (α-amylase) and range of 24.42 to 354.72mg.maltose/min.g (β-amylase) were in beekeepers’ sample, and ranged of 37.71 to 152.52mg.maltose/min.g (α-amylase) and ranged of 31.11 to 161.37mg.maltose/min.g (β-amylase) were in commercial samples, HMF contents of honey from beekeepers were ND~419.17ppm while those of commercial products were 49.44~195.62ppm. The sanitary examinations showed that aerobic plate content were about 0~32 CFU/g in honey from beekeepers, and 0~35 CFU/g in commercial samples.
In honey from beekeepers, except 6 samples, which total contents of fructose and glucose were lowered than 60%, and 4 samples which HMF contents were higher than the CNS indexed value(40ppm), most of the samples were tallied with the A grade of CNS standards. Of those in commercial products, 3 samples of sucrose contents were as high as 8.55%, 19.64%, and 23.45%, and all the samples of HMF contents were failed to met the B grade of CNS standards.
Adulteration inspection included the index of flavonoid, pollen contents and its taxonomy. Naringin, norin, myricetin, kaempferol, apigenin and galangin were identified to be existed in most of the samples from beekeepers, while those of naringin, myricetin, apigenin, quercitrin and galangin were existed in commercial samples. Pollen examination showed contents of pollen were ranged from 1560 to 19240pollen/g in beekeepers’ honey, and 23 families were identified, while those of pollen contents were 0 to 2670pollen/g in commercial samples, and total of 15 families were determined. Briefly, the Sapindaceae (Euphoria longana and Litchi chinensis) was examined to be the predominant pollen in both beekeepers and commercial samples, and secondary pollen were proved to be Cruciferae, Compositae, Euphorbiaceae (Macaranga tanarius and mallotus japonicus) and Ulmaceae (Trema sp.). Only 13.33% in commercial samples met the requirement standard (2000 pollen/g) for real honey, and up to 60% of the inspected samples were shown to have no any pollen existed.
In summary, in order to get the more objective and convincing results, any single index seems not enough to conclude the identity. Alternately, multi-indices matched together will be more precisely to evaluate the adulteration.
目 錄
中文摘要------------------------------------------------------------- I
英文摘要------------------------------------------------------------- IV
誌謝------------------------------------------------------------------- VII
目錄------------------------------------------------------------------- VIII
圖表索引------------------------------------------------------------- XIII
表目---------------------------------------------------------------- XIII
圖目---------------------------------------------------------------- XV
壹、文獻回顧------------------------------------------------------- 1
一、蜂蜜之簡介-------------------------------------------------- 1
1. 蜂蜜之物理特性------------------------------------------ 1
2. 植物花蜜之形成------------------------------------------ 2
(1) 氣溫--------------------------------------------------- 2
(2) 空氣溼度--------------------------------------------- 3
(3) 降雨量------------------------------------------------ 3
(4) 風------------------------------------------------------ 3
(5) 土壤--------------------------------------------------- 3
(6) 花之位置--------------------------------------------- 3
(7) 大小年------------------------------------------------ 3
3. 蜂蜜之蜜源植物------------------------------------------ 4
(1) 主要蜜源植物--------------------------------------- 4
A. 油菜----------------------------------------------- 4
B. 黃荊------------------------------------------------ 4
C. 柑桔------------------------------------------------ 4
D. 荔枝------------------------------------------------ 4
E. 龍眼------------------------------------------------ 5
(2) 一般蜜源植物及輔助蜜源植物------------------- 5
4. 蜂蜜之生產流程------------------------------------------- 8
5. 蜂蜜之組成------------------------------------------------- 10
6. 蜂蜜之產量------------------------------------------------- 13
7. 生產蜂蜜之蜂種------------------------------------------- 13
(1) 黑色蜂------------------------------------------------- 13
(2) 義大利蜂---------------------------------------------- 13
(3) 灰蜂---------------------------------------------------- 14
(4) 高加索蜂---------------------------------------------- 14
8. 蜂蜜之藥理活性及其應用-------------------------------- 14
9. 蜂蜜之抗菌作用及原理----------------------------------- 15
二、蜂蜜之相關研究---------------------------------------------- 18
1. 蜂蜜品質之評估-------------------------------------------- 18
(1) 風味----------------------------------------------------- 18
(2) 揮發性成分-------------------------------------------- 18
(3) 有機酸-------------------------------------------------- 19
(4) 水分----------------------------------------------------- 19
(5) 生菌數-------------------------------------------------- 20
(6) 酵素活性----------------------------------------------- 20
(7) 羥甲基糠醛(5-hydroxymethyl-2-furaldehyde
;HMF)------------------------------------------------- 20
(8) 蜂蜜之結晶------------------------------------------- 24
2. 蜂蜜真偽之鑑定指標------------------------------------- 24
(1) 醣類---------------------------------------------------- 24
(2) 同位素與NMR-------------------------------------- 28
(3) 類黃酮及酚類化合物------------------------------- 28
(4) 花粉---------------------------------------------------- 29
貳、材料與方法----------------------------------------------------- 31
一、材料、藥品及儀器------------------------------------------- 31
1. 材料------------------------------------------------------------ 31
2. 藥品------------------------------------------------------------ 39
3. 儀器------------------------------------------------------------ 39
4. 培養基組成分------------------------------------------------ 39
二、分析方法--------------------------------------------------------- 40
1. 蜂蜜之一般成分分析--------------------------------------- 40
(1) 水分------------------------------------------------------- 40
(2) 粗蛋白---------------------------------------------------- 40
(3) 粗灰分---------------------------------------------------- 41
2. 蜂蜜之微量元素及重金屬含量測定---------------------- 42
3. 蜂蜜之醣類含量測定---------------------------------------- 42
4. 蜂蜜pH值之測定-------------------------------------------- 42
5. 蜂蜜之可滴定酸測定---------------------------------------- 43
6. 蜂蜜之羥甲基糠醛(5-hydroxymethyl-2-furaldehyde,
HMF含量測定--------------------------------------------- 43
7. 蜂蜜中澱粉酶(α及β-amylase)活性之測定---------- 44
(1) 原理----------------------------------------------------- 44
(2) 試劑----------------------------------------------------- 44
(3) 標準溶液之配製-------------------------------------- 45
(4) 反應----------------------------------------------------- 46
(5) 計算----------------------------------------------------- 46
8. 蜂蜜總生菌數之測定-------------------------------------- 46
9. 蜂蜜花粉之萃取與鑑定----------------------------------- 47
(1) 蜂蜜花粉之萃取-------------------------------------- 47
(2) 蜂蜜花粉數量之計算-------------------------------- 47
(3) 蜂蜜花粉之鑑定-------------------------------------- 47
10. 蜂蜜萃取液中類黃酮之鑑定(毛細管電泳法)-------- 48
(1) 標準品溶液之配製----------------------------------- 48
(2) 樣品之製備-------------------------------------------- 49
(3) 標準品及樣品之最適分析條件-------------------- 49
11. 統計分析----------------------------------------------------- 50
參、結果與討論---------------------------------------------------- 51
一、 蜂蜜產品標示之調查----------------------------------- 51
1. 品牌---------------------------------------------------------- 51
2. 製造日期與保存期限------------------------------------- 51
3. 標識---------------------------------------------------------- 52
4. 重量與價格------------------------------------------------- 52
5. 成分說明---------------------------------------------------- 52
二、蜂蜜品質之探討------------------------------------------- 54
1. 蜂蜜之一般組成分分析---------------------------------- 54
(1) 水分---------------------------------------------------- 54
(2) 灰分---------------------------------------------------- 54
(3) 醣類---------------------------------------------------- 57
A. 還原糖-------------------------------------------- 57
B. 蔗糖----------------------------------------------- 57
C. 果糖與葡萄糖比值----------------------------- 58
2. 蜂蜜樣品中礦物質及微量元素之分析----------------- 61
3. pH-------------------------------------------------------------- 64
4. 酸度(可滴定酸)---------------------------------------------- 64
5. HMF----------------------------------------------------------- 67
6. 澱粉酶活性之探討----------------------------------------- 70
7. 總生菌數之調查-------------------------------------------- 71
8. 蜂蜜結晶之觀察-------------------------------------------- 72
三、蜂蜜真偽鑑定之探討---------------------------------------- 77
1. 蜂蜜中類黃酮物質之分析-------------------------------- 77
2. 蜂蜜中總花粉數含量之測定----------------------------- 90
3. 蜂蜜花粉之鑑定-------------------------------------------- 90
四、綜合評估蜂蜜之品質與真偽------------------------------- 103
肆、結論-------------------------------------------------------------- 104
伍、參考文獻------------------------------------------------------ 108
表 目
表一、台灣之重要蜜源植物--------------------------------------- 6
表二、市售蜂蜜之組成--------------------------------------------- 11
表三、蜂蜜中礦物質及維生素之含量--------------------------- 12
表四、蜂蜜的酵素活性--------------------------------------------- 21
表五、蜂蜜之中國國家標準--------------------------------------- 23
表六、蜂蜜之寡糖成分--------------------------------------------- 26
表七、16件蜂農蜜樣品之性狀描述----------------------------- 32
表八、15件市售蜂蜜樣品之性狀描述-------------------------- 33
表九、蜂農蜜樣品之水分、灰分及蛋白質含量--------------- 55
表十、市售蜂蜜樣品之水分、灰分及蛋白質含量------------ 56
表十一、蜂農蜜樣品中不同醣類之含量及其相互比值------ 59
表十二、市售蜂蜜樣品中不同醣類之含量及其相互比值--- 60
表十三、蜂農蜜樣品中主要礦物質及微量元素之含量------- 62
表十四、市售蜂蜜樣品中主要礦物質及微量元素之含量--- 63
表十五、蜂農蜜樣品之pH及其可滴定酸含量---------------- 65
表十六、市售蜂蜜樣品之pH及其可滴定酸含量------------- 66
表十七、蜂農蜜樣品之HMF含量------------------------------- 68
表十八、市售蜂蜜樣品之HMF含量---------------------------- 69
表十九、蜂農蜜樣品之澱粉酶活性測試------------------------ 73
表二十、市售蜂蜜樣品之澱粉酶活性測試--------------------- 74
表二十一、蜂農蜜樣品之總生菌數含量------------------------ 75
表二十二、市售蜂蜜樣品之總生菌數含量--------------------- 76
表二十三、以CZE測定蜂農蜜中可鑑定出之類黃酮種類-- 88
表二十四、以CZE測定市售蜂蜜中可鑑定出之類黃酮種類- 89
表二十五、蜂農蜜樣品之花粉數----------------------------------- 91
表二十六、市售蜂蜜樣品之花粉數------------------------------- 92
表二十七、綜合蜂農蜜之各項分析數值------------------------- 106
表二十八、綜合市售蜂蜜之各項分析數值--------------------- 107
圖 目
圖一、市售蜂蜜之生產流程-------------------------------------- 9
圖二、蜂蜜中D-gluconic acid之形成機制-------------------- 17
圖三、羥甲糠醛之形成途徑-------------------------------------- 22
圖四、蜂農蜜產地分佈圖----------------------------------------- 34
圖五、16件蜂農蜜樣品外貌圖---------------------------------- 35
圖六、15件市售蜂蜜樣品外貌圖------------------------------- 37
圖七、十一種類黃酮標準品在0.1M H3BO3 (pH 9.5)-5%
甲醇緩衝液之毛細管區帶電泳層析圖---------------- 78
圖八、以毛細管區帶電泳測定蜂農蜜中之類黃酮物質---- 80
圖九、以毛細管區帶電泳測定市售蜂蜜中之類黃酮物質- 84
圖十、蜂農蜜樣品之花粉種類及其分佈情形----------------- 94
圖十一、市售蜂蜜樣品之花粉種類及其分佈情形----------- 97
圖十二、蜂農蜜與市售蜂蜜樣品中存在之花粉種類-------- 99
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