【作者】 刘红；

【导师】 欧仕益；

【作者基本信息】 暨南大学 ， 食品科学， 2007， 硕士

【摘要】 本文采用葡萄糖分别与天冬酰氨和甘氨酸在160℃下反应建立美拉德反应的模拟体系，采用高效液相色谱(HPLC)、荧光分光光度法和离子色谱法等研究了抗氧化剂丁基羟基茴香醚(BHA)、二丁基羟基甲苯(BHT)、特丁基对苯二酚(TBHQ)、维生素C(Vc)对美拉德反应产物的影响。1．在同一色谱条件下，采用高效液相色谱分离测定美拉德反应产物，比较空白与添加不同抗氧化剂在同一检测波长下色谱峰的出峰数以及峰面积的差异。结果表明：抗氧化剂对HPLC色谱峰的出峰数、峰面积都有显著影响；在相同条件下，对甘氨酸-葡萄糖体系影响更显著。2．添加抗氧化剂对天冬酰氨—葡萄糖体系的褐变程度(稀释15倍，420nm处测定光吸收值)没有显著影响，但对甘氨酸—葡萄糖体系的影响显著。3．采用荧光分光光度计在激发波长419nm,发射波长507nm下测定美拉德反应产物(MRPs)的荧光强度，结果表明：MRPs的荧光强度随着抗氧化剂浓度的增加而增加，其中甘氨酸—葡萄糖体系的荧光强度显著大于天冬酰氨—葡萄糖体系。4．采用离子色谱法测定添加不同抗氧化剂对美拉德反应产物中氨基酸和糖种类与含量的影响。结果表明，添加抗氧化剂对其氨基酸的种类与含量都有显著影响。在天冬酰氨-葡萄糖体系中，未添加抗氧化剂的产生了4种氨基酸，分别是赖氨酸、组氨酸、苯丙氨酸、谷氨酸；添加BHA产生了4种氨基酸，分别是组氨酸、天冬氨酸盐、苯丙氨酸、精氨酸；添加BHT产生了4种氨基酸，分别是赖氨酸、组氨酸、谷氨酸、丙氨酸；添加TBHQ产生了7种氨基酸，分别是赖氨酸、组氨酸、苯丙氨酸、天冬氨酸盐、谷氨酸、丝氨酸、酪氨酸；添加Vc产生了5种氨基酸，分别是赖氨酸、组氨酸、苯丙氨酸、谷氨酸、精氨酸。在甘氨酸-葡萄糖体系中，未添加抗氧化剂的产生了6种氨基酸，分别是丙氨酸、脯氨酸、组氨酸、苯丙氨酸、谷氨酸、酪氨酸；添加BHA的产生了4种氨基酸，分别是组氨酸、脯氨酸、谷氨酸、酪氨酸；添加BHT的产生了5种氨基酸，分别是组氨酸、谷氨酸、酪氨酸、丝氨酸、精氨酸；添加TBHQ的产生了9种氨基酸，分别是丙氨酸、组氨酸、苯丙氨酸、谷氨酸、缬氨酸、精氨酸、丝氨酸、赖氨酸、亮氨酸；添加Vc产生了6种氨基酸，分别是脯氨酸、组氨酸、苯丙氨酸、谷氨酸、酪氨酸、赖氨酸。而当反应体系中不添加糖时，单独BHA与天冬酰氨油浴后检测到天冬酰氨、组氨酸与赖氨酸；Vc与天冬酰氨油浴后都检测到天冬酰氨与组氨酸；BHT、TBHQ与天冬酰氨油浴后只检测到天冬酰氨；BHA与甘氨酸、Vc与甘氨酸油浴后都检测到甘氨酸与组氨酸；BHT、TBHQ与甘氨酸油浴后只检测到甘氨酸。当反应体系中不添加氨基酸时，所有抗氧化剂与葡萄糖油浴后都没有检测到氨基酸，这些结果说明新的氨基酸通过美拉德反应产生，并且氨基酸种类的不同会影响其产生氨基酸的种类与含量，添加不同种类的抗氧化剂对美拉德反应产物中氨基酸的种类和含量也有显著影响。5．添加抗氧化剂对产生的单糖种类和含量都有显著影响。在天冬酰氨—葡萄糖体系中，添加BHT产生三种糖：果糖、阿拉伯糖、甘露醇或木糖；添加TBHQ产生了果糖、阿拉伯糖；添加BHA产生了半乳糖：添加Vc与未添加抗氧化剂的都没有产生新糖。在甘氨酸—葡萄糖体系中，添加BHT产生三种糖：果糖、阿拉伯糖、甘露醇或木糖；未添加抗氧化剂的与添加Vc的检测到果糖与葡萄糖；其余的只检测到葡萄糖。说明添加不同种类的抗氧化剂对美拉德反应产物中糖的种类和含量都有影响，并且氨基酸种类对美拉德反应产物中糖的种类和含量也有显著影响。在抗氧化剂-葡萄糖体系中，添加BHA与BHT产生了鼠李糖、果糖；添加TBHQ与Vc未产生新糖，而在抗氧化剂—氨基酸体系中未产生任何的糖类。说明尽管抗氧化剂-葡萄糖单独油浴会产生新糖，但是添加氨基酸发生美拉德反应后其糖类也会发生显著影响。更多还原

【Abstract】 The effects of butyl hydroxy aniso (BHA), dibutyl hydroxy toluene (BHT), tertiary butylhydroquinone (TBHQ), L-ascorbic acid (Vc) on maillard reaction products (MRPs) were respectively tested in asparagines-glucose and glycine-glucose reaction system at 160℃using HPLC, colour determination, fluorescence spectrophotometry and ion-chromatogram.1. MRPs were tested by HPLC at the same chromatogram condition. The results showed that the number of peaks, the area of total peaks and single peak were greatly influenced by the antioxidants; and the species and contents of MPRs were more influenced by the antioxidants in glycine-glucose reaction system than in asparagines-glucose reaction system.2. The browning of Maillard reaction products were tested spectrophotometrically at 420nm after diluting 15 times. The results showed that the OD420 of MRPs in asparagines-glucose reaction system is higher than in glycine-glucose reaction system, and OD420 of MRPs were more influenced by the antioxidants in glycine-glucose reaction system than that in asparagines-glucose reaction system at the same condition.3. The fluorescence of MRPs were tested at an excitation wavelength of 419nm and an emission wavelength of 507nm. The results showed that the fluorescence intensity were greatly increased by the addition of antioxidants; and the fluorescence of MRPs were more influenced by the antioxidants in glycine-glucose reaction system than that in asparagines-glucose reaction system at the same condition. The fluorescence intensity increased as the concentration of antioxidant increased.4. The effects of antioxidants on amino acids and sugars of MRPs were determined by ion-chromatogram. The results showed that the speicies and contents of amino acids were greatly influenced by the antioxidants.In asparagines-glucose reaction system, there are four new kinds of amino aicds (lysine, histidine, phenylalanine, glutamic acid) were produced when no antioxidants was added; while there are four (histidine, aspartate, phenylalanine, arginine), four (lysine, histidine, glutamicacid, alanine), seven (lysine, histidine, phenylalanine, aspartate, glutamic acid, serine, tyrosine) and five (lysine, histidine, phenylalanine, glutamic acid, arginine) new kinds of amino acids were produced when BHA, BHT, TBHQ and V_c were respectively added. In glycine-glucose reaction system, there are six new kinds of amino aicds (alanine, proline, histidin, phenylalanine, glutamic acid, tyrosine) were produced when no antioxidants was added; while there are four (histidine, proline, glutamic acid, tyrosine), five(histidine, glutamic acid, tyrosine, serine, arginine), nine(alanine, histidine, phenylalanine, glutamic acid, valine, arginine, serine, lysine, leucine), and six (proline, histidine, phenylalanine, glutamic acid, tyrosine, lysine) new kinds of amino acids were produced when BHA, BHT, TBHQ and V_c were respectively added.There are two (histidine, lysine), one (histidine) new kinds of amino aicds were produced in antioxidant-asparagines reaction system when BHA and V_c were respectively added; while there is no new kinds of amino aicds were produced in antioxidant-asparagines reaction system when BHT and TBHQ were respectively added. In antioxidant-glycine reaction system ,there are one (histidine) new kinds of amino aicds were produced when BHA and Vc were respectively added; while there is no new kinds of amino aicds were produced in antioxidant-asparagines reaction system when BHT and TBHQ were respectively added.However, there are no amino acids produced in antioxidant-glucose reaction system.These results showed that new amino acids were produced in maillard-reaction, and the kinds and content of the new amino acids were greatly influenced the added amino acids and antioxidants.5. The speicies and contents of sugars in MRPs were greatly influenced by the antioxidants. In asparagines-glucose reaction system, there are three (fructose, arabinose, xylose or mannose), two (fructose and arabinose), one (galactose) new kinds of sugars were produced when BHT, TBHQ and BHA were respectively added,but there are no new sugars produced when no antioxidants and V_c was added. In glycine-glucose reaction system, there are three(fructose, arabinose, xylose or mannose) new kinds of sugars were produced when BHT were added, and there is one(fructose) new kinds of sugars were produced when no antioxidants and V_c was added. These results showed that the speicies and contents of sugars were also greatly influenced by the added amino acids and antioxidants.In antioxidants-glucose reaction system, there are two new kinds of sugars (ramnose and fructose) were produced when BHA and BHT were added,but there are no new sugars produced when other antioxidants were added.. It Was concluded that there are new kinds of sugars were produced in antioxidants-glucose reaction system, and the speicies and contents of sugars were greatly influenced by maillard-reaction when amino acids were added.更多还原