卡拉胶和褐藻胶流变学特性及凝胶特性的研究
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摘要
褐藻胶和卡拉胶是从海藻中提取的两种多糖,在食品中具有良好的应用前景。本论文以卡拉胶和褐藻胶为研究对象,进行了以下几个方面的研究:
1)两种海藻胶溶液流变学特性的研究。结果表明卡拉胶和褐藻胶溶液在一定的温度下均为假塑性流体,其流动曲线与power law模型具有较好相关性;在低频率区域,这两种海藻胶以粘性为主,在高频率区域以弹性为主。当浓度为时2.0%,二者都有明显的触变性,随着二者浓度降低,溶液的触变性逐渐减弱。
2)两种海藻胶凝胶特性的研究。
卡拉胶凝胶是热可逆凝胶,在升降温过程中有明显的热滞后现象。当凝胶时间为8小时时凝胶强度最大;KCl浓度对其凝胶强度有较大影响,随着KCl浓度的增加凝胶强度呈先增加后减少的趋势,浓度为0.8%时凝胶强度最大。
褐藻胶凝胶是非可逆凝胶,在氯化钙体系中,氯化钙浓度、温度及褐藻胶M/G对凝胶性能有很大的影响;当氯化钙温度为50℃、浓度为2.0%时,凝胶的拉伸强度和吸水性能最佳;高G型褐藻酸钙凝胶拉伸强度优于高M型,但吸水性能比较差;红外光谱结果表明,褐藻胶成凝胶后,-OH峰向高波数方向偏移并且C-H伸缩振动变弱。
在葡萄糖醛酸内酯体系中,褐藻胶凝胶结构比较均匀,但Ca2+浓度、M/G比以及葡萄糖醛酸内酯对其性质影响较大。随着钙离子浓度的增加,体系凝胶时间逐渐缩短,而贮藏模量G′、损耗模量G″、复合粘度、凝胶强度逐渐增大;随着M/G比增加,G′、G″和凝胶强度都逐渐减少,而tanδ和凝胶时间逐渐增加;随着葡萄糖醛酸内酯的增加,凝胶时间逐渐缩短,但对稳定后凝胶的G′、G″和凝胶强度影响不大。3)两种海藻胶与其他胶体协同作用的研究。
卡拉胶与魔芋胶之间有协同增效的作用,所形成的凝胶具有热可逆性,并且胶凝点低于熔化点。随着魔芋胶量的增加,混合凝胶的G′和G″、凝胶强度、胶凝点和熔化点都有先增大后降低的趋势,当卡拉胶与魔芋胶比为7:3时最大;在酸性条件下蔗糖对体系的凝胶强度保护作用,KCl浓度为0.5%时,凝胶强度最大。红外光谱结果表明,卡拉胶与魔芋胶混合形成凝胶后,-OH峰向低波数方向偏移。
褐藻胶与高甲氧基果胶之间有增效的协同作用,二者的混合比、褐藻胶M/G比以及蔗糖对其凝胶性质影响比较大;当两者质量比为3:2时,凝胶强度最大;褐藻胶M/G比越小,混合凝胶的G′和G″越大,tanδ越小,与频率的相关性越低。添加适量的蔗糖可增加体系的凝胶强度。红外光谱结果表明,褐藻胶和高甲氧基果胶形成凝胶后,-OH峰高波数方向偏移,并且C-H和C=O伸缩振动变弱。
Carrageenan and algin are two kinds of polysaccharides which are extracted from the seaweed, and they had broad applications in food. The object of this thesis is to study the rheological and gel properties of algin and carrageenan. The main results are as follows:
1) Study on the rheological properties of the aqueous solution of carrageenan and algin:
The results showed that carrageenan and algin were both pseudoplastic fluid and their flow curve had a good correlation with the power law model. In the low-frequency region, they mainly exhibited viscous, while in the high frequency region mainly flexibility. When the concentration was 2.0%, they both had thixotropy, and the lower the concentration was, the smaller the thixotropic central was.
2) Study on the gelling properties of carrageenan and algin.
Carrageenan was a hot reversible gel, and it had the thermal hysteresis significantly in the process of heating and cooling.The maximum gel strength was found when the gelling time was 8h .The KCl concentration had great effect on gel strength, with the KCl concentration increasing, the gel strength firstly increased and then reduced, the maximum gel strength was found when the content of KCl was 0.8%.
Alginate gel was a non-reversible gel.In the system of CaCl2,the content of CaCl2,temperature of CaCl2 and the composition of mannuronic acid / guluronic acid ( M/G) had made difference on the properties of alginate calcium gel .The texisle strength and absorbency ability of gel was the best when the content of CaCl2 and the temperature of CaCl2 was 2.0% and 50℃respectively; The texisle strength of alginate calcium by high G algin was better than that of by high M, while the absorbency ability of water by high G was smaller than that of high M. The IR spectra results showed that the loacation of -OH peak migrated to the high wavenumber and C-H stretching weak, when alginate sodium changed into alginate calcium.
In GDL system, the gel structure was more uniform, but the concentration of Ca2+ and GDL and the M / G ratio had great effect on the gel properties. The storage modulus, loss modulus, complex viscosity, gel strength gradually increased with the increasing of calcium concentration, while the gel time gradually decreased. As the M / G ratio increased, the storage modulus, loss modulus and gel strength diminished, while tanδand gel time gradually increased.
3) Study on the synergy of algin, carrageenan and other gel.
Synergy was between carrageenan and konjac gum, and the mixture was a kind of heat reversible gel, the melt temperature was higher than the gel temperature. The G′and G″,gel strength ,the gel point and melt point increased at first and then decreased with the content of konjac gum increasing, the maximum synergy was found when carrageenan/ konjac gum was7:3. In addition , pH、sugar and the concentration of KCl had some effect on gel strength, sugar could protect the gel strength in low pH, and the gel strength firstly increased and then decreased with the content of KCl increasing, the maximum was found when the content of KCl was 0.5%. The IR spectra results showed changes were-OH peak migration to the low wavenumber during the gel formation .
5 Algin could interact with high-methoxy pectin to form gel, the gel strength was the maximum when the ratio is 3:2.The storage modulus, loss modulus had great relevance with oscillation frequency, and with the M / G ratio of algin decreasing, the relevance was lower. In the same frequency, the storage modulus and loss modulus of by high G was greater than of by high M; while the tanδof by high G was smaller. The addition of sucrose could increase the gel strength properly. The IR spectra results showed that the major structural changes were-OH peak migration to the high wavenumber and C-H and C = O stretching weak during the gel formation.
1)两种海藻胶溶液流变学特性的研究。结果表明卡拉胶和褐藻胶溶液在一定的温度下均为假塑性流体,其流动曲线与power law模型具有较好相关性;在低频率区域,这两种海藻胶以粘性为主,在高频率区域以弹性为主。当浓度为时2.0%,二者都有明显的触变性,随着二者浓度降低,溶液的触变性逐渐减弱。
2)两种海藻胶凝胶特性的研究。
卡拉胶凝胶是热可逆凝胶,在升降温过程中有明显的热滞后现象。当凝胶时间为8小时时凝胶强度最大;KCl浓度对其凝胶强度有较大影响,随着KCl浓度的增加凝胶强度呈先增加后减少的趋势,浓度为0.8%时凝胶强度最大。
褐藻胶凝胶是非可逆凝胶,在氯化钙体系中,氯化钙浓度、温度及褐藻胶M/G对凝胶性能有很大的影响;当氯化钙温度为50℃、浓度为2.0%时,凝胶的拉伸强度和吸水性能最佳;高G型褐藻酸钙凝胶拉伸强度优于高M型,但吸水性能比较差;红外光谱结果表明,褐藻胶成凝胶后,-OH峰向高波数方向偏移并且C-H伸缩振动变弱。
在葡萄糖醛酸内酯体系中,褐藻胶凝胶结构比较均匀,但Ca2+浓度、M/G比以及葡萄糖醛酸内酯对其性质影响较大。随着钙离子浓度的增加,体系凝胶时间逐渐缩短,而贮藏模量G′、损耗模量G″、复合粘度、凝胶强度逐渐增大;随着M/G比增加,G′、G″和凝胶强度都逐渐减少,而tanδ和凝胶时间逐渐增加;随着葡萄糖醛酸内酯的增加,凝胶时间逐渐缩短,但对稳定后凝胶的G′、G″和凝胶强度影响不大。3)两种海藻胶与其他胶体协同作用的研究。
卡拉胶与魔芋胶之间有协同增效的作用,所形成的凝胶具有热可逆性,并且胶凝点低于熔化点。随着魔芋胶量的增加,混合凝胶的G′和G″、凝胶强度、胶凝点和熔化点都有先增大后降低的趋势,当卡拉胶与魔芋胶比为7:3时最大;在酸性条件下蔗糖对体系的凝胶强度保护作用,KCl浓度为0.5%时,凝胶强度最大。红外光谱结果表明,卡拉胶与魔芋胶混合形成凝胶后,-OH峰向低波数方向偏移。
褐藻胶与高甲氧基果胶之间有增效的协同作用,二者的混合比、褐藻胶M/G比以及蔗糖对其凝胶性质影响比较大;当两者质量比为3:2时,凝胶强度最大;褐藻胶M/G比越小,混合凝胶的G′和G″越大,tanδ越小,与频率的相关性越低。添加适量的蔗糖可增加体系的凝胶强度。红外光谱结果表明,褐藻胶和高甲氧基果胶形成凝胶后,-OH峰高波数方向偏移,并且C-H和C=O伸缩振动变弱。
Carrageenan and algin are two kinds of polysaccharides which are extracted from the seaweed, and they had broad applications in food. The object of this thesis is to study the rheological and gel properties of algin and carrageenan. The main results are as follows:
1) Study on the rheological properties of the aqueous solution of carrageenan and algin:
The results showed that carrageenan and algin were both pseudoplastic fluid and their flow curve had a good correlation with the power law model. In the low-frequency region, they mainly exhibited viscous, while in the high frequency region mainly flexibility. When the concentration was 2.0%, they both had thixotropy, and the lower the concentration was, the smaller the thixotropic central was.
2) Study on the gelling properties of carrageenan and algin.
Carrageenan was a hot reversible gel, and it had the thermal hysteresis significantly in the process of heating and cooling.The maximum gel strength was found when the gelling time was 8h .The KCl concentration had great effect on gel strength, with the KCl concentration increasing, the gel strength firstly increased and then reduced, the maximum gel strength was found when the content of KCl was 0.8%.
Alginate gel was a non-reversible gel.In the system of CaCl2,the content of CaCl2,temperature of CaCl2 and the composition of mannuronic acid / guluronic acid ( M/G) had made difference on the properties of alginate calcium gel .The texisle strength and absorbency ability of gel was the best when the content of CaCl2 and the temperature of CaCl2 was 2.0% and 50℃respectively; The texisle strength of alginate calcium by high G algin was better than that of by high M, while the absorbency ability of water by high G was smaller than that of high M. The IR spectra results showed that the loacation of -OH peak migrated to the high wavenumber and C-H stretching weak, when alginate sodium changed into alginate calcium.
In GDL system, the gel structure was more uniform, but the concentration of Ca2+ and GDL and the M / G ratio had great effect on the gel properties. The storage modulus, loss modulus, complex viscosity, gel strength gradually increased with the increasing of calcium concentration, while the gel time gradually decreased. As the M / G ratio increased, the storage modulus, loss modulus and gel strength diminished, while tanδand gel time gradually increased.
3) Study on the synergy of algin, carrageenan and other gel.
Synergy was between carrageenan and konjac gum, and the mixture was a kind of heat reversible gel, the melt temperature was higher than the gel temperature. The G′and G″,gel strength ,the gel point and melt point increased at first and then decreased with the content of konjac gum increasing, the maximum synergy was found when carrageenan/ konjac gum was7:3. In addition , pH、sugar and the concentration of KCl had some effect on gel strength, sugar could protect the gel strength in low pH, and the gel strength firstly increased and then decreased with the content of KCl increasing, the maximum was found when the content of KCl was 0.5%. The IR spectra results showed changes were-OH peak migration to the low wavenumber during the gel formation .
5 Algin could interact with high-methoxy pectin to form gel, the gel strength was the maximum when the ratio is 3:2.The storage modulus, loss modulus had great relevance with oscillation frequency, and with the M / G ratio of algin decreasing, the relevance was lower. In the same frequency, the storage modulus and loss modulus of by high G was greater than of by high M; while the tanδof by high G was smaller. The addition of sucrose could increase the gel strength properly. The IR spectra results showed that the major structural changes were-OH peak migration to the high wavenumber and C-H and C = O stretching weak during the gel formation.
引文
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[13] Paula M. Gilsenan, Simon B. Ross-Murphy.Shear creep of gelatin gels from mammalian and piscine collagens.International Journal of Biological Macromolecules,2001,29: 53-61
[14] Phillippa Rayment, Simon B. Ross-Murphy, Peter R.Rheological properties of guargalactomannan and rice starch mixtures. II. Creep measurements. Carbohydrate Polymers ,1998,35:55-63
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[17]魏德卿,夏怡,旷文峰.高分子学报(Acta PolymericaSinica),1997,(4): 404～409.
[1]邝生鲁编.现代精细化工高新技术与产品的合成工艺.北京:科学技术文献出版社,1997,574-575
[2]谢平.海藻酸及其盐的食用和药用价值.开封医专学报,1997,16(4):28-31
[3]李安平.人心果乳汁的流变学特性.中南林学院学报,2005, 4 (25) : 88
[4] C. Michon. Structure evolution of carrageenan /milk gels: effect of shearing, carrageenan concentration and nufraction on rheological behavior. Food Hydrocolloids , 2005, 3 (19) : 544
[5] Rodriguez.Hernandez A I , Tecante A. Dynamic viscoelastic behavior of gellan-ι-carrageenan and gellan-xanthan gels,Food Hydrocollids , 1999 ,13 :59 - 64.
[6]过菲,许时婴.羊栖菜多糖中褐藻酸钠溶液的流变性质和胶凝性质无锡轻工业大学学报,2003,22(2):93-97
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[1]刘凌,薛毅,王亚南,等.κ-卡拉胶胶凝特性研究.郑州轻工业学院学报,1999,14(1):64-68
[2]Yu Chen,Ming Long Liao,Dave.E.Dunsan. The Rheology of K+-κ-carrageenan as a weak gel.Carbohydrate Polymers,2002,50:109-116
[3]许时婴,钱和,魔芋葡甘露聚糖的化学结构与流变性质.无锡轻工业学院学报, 1991,10(1): 1- 12.
[4]汪超,李斌,徐潇,等.魔芋葡甘聚糖的流变特性研究.农业工程学报,2005,21(8):157-160
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[9]詹永,杨,勇.复配魔芋胶凝胶特性的影响因素.中国食品添加剂,2005,3:61-67
[10] S.Y. Hsu , H.-Y. Chung.Interactions of konjac, agar, curdlan gum, j-carrageenan and eheating treatment in emulsified meatballs. Journal of Food engineering ,2000,44: 199-204
[11]何曼君,陈维孝,董西侠.高分子物理.上海:复旦大学出版社,2000.
[12] P. Penroja, J.R. Mitchellb,, S.E. Hillb. Effect of konjac glucomannan deacetylation on the properties of gels ormed from mixtures of kappa carrageenan and konjac glucomannan . Carbohydrate Polymers , 2005 ,59:367–376
[13] Paula M. Gilsenan, Simon B. Ross-Murphy.Shear creep of gelatin gels from mammalian and piscine collagens.International Journal of Biological Macromolecules,2001,29: 53-61
[14] Phillippa Rayment, Simon B. Ross-Murphy, Peter R.Rheological properties of guargalactomannan and rice starch mixtures. II. Creep measurements. Carbohydrate Polymers ,1998,35:55-63
[15] A.B. Rodda, C.R. Davisb, D.E. Dunstana.Rheological characterisation of‘weak gel’carrageenan stabilised milks. Food Hydrocolloids,2000,19:445-454
[16]金竣,林美娇.海藻利用与加工.北京:科学出版社,1993
[17]魏德卿,夏怡,旷文峰.高分子学报(Acta PolymericaSinica),1997,(4): 404～409.
[1]邝生鲁编.现代精细化工高新技术与产品的合成工艺.北京:科学技术文献出版社,1997,574-575
[2]谢平.海藻酸及其盐的食用和药用价值.开封医专学报,1997,16(4):28-31
[3]李安平.人心果乳汁的流变学特性.中南林学院学报,2005, 4 (25) : 88
[4] C. Michon. Structure evolution of carrageenan /milk gels: effect of shearing, carrageenan concentration and nufraction on rheological behavior. Food Hydrocolloids , 2005, 3 (19) : 544
[5] Rodriguez.Hernandez A I , Tecante A. Dynamic viscoelastic behavior of gellan-ι-carrageenan and gellan-xanthan gels,Food Hydrocollids , 1999 ,13 :59 - 64.
[6]过菲,许时婴.羊栖菜多糖中褐藻酸钠溶液的流变性质和胶凝性质无锡轻工业大学学报,2003,22(2):93-97
[7]何曼君,陈维孝,董西侠.高分子物理.上海:复旦大学出版社,2000:235-240
[8]代欣欣,李汴生.食品增稠剂流变学研究综述.中国食品添加剂, 2007 ,4:138-142
[9]李里特.食品物性学.北京:中国农业出版社, 2001: 16-26.
[10]江体乾.化工流变学.上海:华东理工大学出版社, 2004: 212-220.
[11]申瑞玲,姚惠源.裸燕麦麸β-葡聚糖的流变学特性及凝胶形成.无锡轻工业大学学报,2005,24(1):41-44
[12]周宇英,唐伟强.食品流变特性研究的进展.粮油加工与食品机械,2001,8:7-9
[13]李辉芹,巩继贤.可生物降解的海藻酸盐凝胶及应用,新纺织,2002(1):35- 37.
[14]秦益民.甲壳胺和海藻酸凝胶在医用敷料中的应用.针织工业,2004(l0):60- 63.
[15]刘昌龄译.海藻酸盐凝胶和绷带.印染译丛,2000(4):99-103.
[16]秦益民.海藻酸凝胶在医敷用料中的应用.合成凝胶,2003,4:11-13.
[17]展义臻,朱平,张建波,郭小青.海藻凝胶在医疗和防护纺织品中的应用.染整技术,2006,28(5):1-6.
[18] David P Tong. Process for the Production of Alginate Fiber Material and Products Made Therefrom,American .Patent, 4562110
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