慢消化淀粉的制备及性质研究
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摘要
慢消化淀粉(SDS,slowly digestible starch)是指在人体小肠中能被完全消化但速度比较慢的一种淀粉,一般是指20～120min内消化的淀粉。国内外制备SDS的方法主要有酶学、物理和化学改性三类方法。本文以蜡质玉米淀粉为原料,系统研究了普鲁兰酶脱支重结晶处理、辛烯基琥珀酸酯化和水热处理方法对SDS形成的影响,并对性质和机理进行深入研究。
第一种方法普鲁兰酶脱支重结晶,主要研究的是普鲁兰酶用量、脱支时间和重结晶时间对SDS形成的影响。当普鲁兰酶浓度20ASPU/g,脱支6h,在4℃条件下放置3d后,SDS含量达到21.26%。扫描电镜观察显示淀粉颗粒形貌变化很大,淀粉颗粒结构消失,呈不规则碎片。脱支重结晶后的淀粉样品晶型发生了变化,从A型晶体变成B型。与原淀粉相比,SDS的热力学参数To、Tp、Tc均升高,△H显著降低,而且随着SDS含量增加,变化越明显。
第二种方法采用辛烯基琥珀酸酐对蜡质玉米淀粉进行酯化处理。辛烯基琥珀酸基团空间位阻效应对酶的阻碍作用有利于SDS的形成,而且随着取代度的升高,SDS含量增加,消化性下降,当取代度为0.0218时,酯化淀粉中SDS含量为20.40%。酯化淀粉溶解度和膨胀度变大,起糊温度降低,糊粘度显著提高。热力学性质研究表明To、Tp、Tc以及热焓值△H均下降。X-射线衍射表明不同取代度的OSA淀粉的晶型仍为A型结晶图谱。
第三种方法采用湿热处理和退火处理两种水热处理(Hydrothermal Treatment),方法。退火处理主要研究了温度、水分含量和时间对SDS形成的影响。淀粉水分含量为60%,在55℃下反应36h,样品中SDS含量达到8.35%。由于热量和水分的长时间作用,使淀粉颗粒内部的结晶结构更完美,提高SDS含量,降低淀粉的消化性。湿热处理主要研究温度、水分含量和时间对SDS形成的影响。淀粉经过湿热处理后,消化性降低,当水分含量35%,温度120℃,时间为10h,SDS含量达9.25%。湿热处理对淀粉颗粒形貌影响不大,与原淀粉相比湿热处理淀粉膨胀度变小,糊粘度下降,起糊温度升高,糊化困难。湿热处理后To、Tp、Tc均上升,淀粉的晶型没有改变。
通过系统研究三种制备方法对淀粉性质、SDS含量和淀粉消化性的影响,认为普鲁兰酶脱支重结晶处理淀粉得到的SDS含量最高,是一种有潜力的制备SDS的方法。
Slowly digestible starches were defined as starches which were digested completely in small intestine of human, between 20 to 120 minutes, but the speed was slow. At present people prepared SDS mainly by enzyme, physical and chemical methods. This paper used waxy corn starch as material systemly studied to prepare SDS by debranching enzyme and recrystallization, octenyl succinic anhydride modifying, and hydrothermal treatment, then researched properties and mechanism of SDS.
Firstly, SDS was prepared by Pullulanase debranching then recrystaled. The effects of amount of Pullulanase, debranched time and recrystallization time on SDS content were studied. When concentration of Pullulanase was 20ASPU/g, debranched time was 6 hour and storaged 3 days at 4℃, content of SDS was 21.26%. The properties of SDS were determined by Scanning Electron Microscopy (SEM), x-ray dirffaction and Differential Scanning Calorimeter (DSC). Results showed that starch granule appearance changed remarkly and structure disappeared. Compared with native starch, crystal form of starch changed from A to B type, besides, DSC determination showed that To、Tp、Tc all increased,△H decreased remarkly, and these change had good relation with SDS content.
Secondly, SDS was prepared by octenyl succinic anhydride modifying. Researches showed that introduced big chemical group in favour of SDS formation by hindering enzymolysis, in addition, SDS content increased and digestibility reduced constantly as the degree of substitution improved. Compared with native starch, these modified starches had low pasting temperature, high peak viscosity, solubility and degree of swelling improved a lot. Besides, thermal parameters such as To、Tp、Tc and△H all reduced. Esterified starches still maintained A type crystal structure.
Thirdly, SDS was prepared by two kinds of hydrothermal treatment such as Annealing and Heat-Moisture Treatment (HMT). The effects of temperature, moisture and time on SDS content by annealing were investigated, and concluded that SDS content reach up to 8.35% when moisture was 60%, temperature 55℃and action time was 36 hours. Annealing changed starches’properties obviously, improved SDS content and reduced digestibility because of long time hydrothermal treatment. As far as HMT was concerned, the effect of treatment temperature, moisture and time on SDS content were also studied, when moisture was 35%, temperature 120℃and treated time was 10 hours, SDS got 9.25% maximum, reduce digestibility remarkly by generating SDS and Resistant Starches. Compared with native starch, HMT made swelling power, viscosity reduce, pasting temperature, To、Tp and Tc increase, but didn’t change crystal structure.
In conclution, by studying these three kinds of preparing methods on SDS content and starch digestibility. Considered that method of enzyme-debranching and recrystallization could achieve a good deal of SDS, which was very potential for SDS preparation.
第一种方法普鲁兰酶脱支重结晶,主要研究的是普鲁兰酶用量、脱支时间和重结晶时间对SDS形成的影响。当普鲁兰酶浓度20ASPU/g,脱支6h,在4℃条件下放置3d后,SDS含量达到21.26%。扫描电镜观察显示淀粉颗粒形貌变化很大,淀粉颗粒结构消失,呈不规则碎片。脱支重结晶后的淀粉样品晶型发生了变化,从A型晶体变成B型。与原淀粉相比,SDS的热力学参数To、Tp、Tc均升高,△H显著降低,而且随着SDS含量增加,变化越明显。
第二种方法采用辛烯基琥珀酸酐对蜡质玉米淀粉进行酯化处理。辛烯基琥珀酸基团空间位阻效应对酶的阻碍作用有利于SDS的形成,而且随着取代度的升高,SDS含量增加,消化性下降,当取代度为0.0218时,酯化淀粉中SDS含量为20.40%。酯化淀粉溶解度和膨胀度变大,起糊温度降低,糊粘度显著提高。热力学性质研究表明To、Tp、Tc以及热焓值△H均下降。X-射线衍射表明不同取代度的OSA淀粉的晶型仍为A型结晶图谱。
第三种方法采用湿热处理和退火处理两种水热处理(Hydrothermal Treatment),方法。退火处理主要研究了温度、水分含量和时间对SDS形成的影响。淀粉水分含量为60%,在55℃下反应36h,样品中SDS含量达到8.35%。由于热量和水分的长时间作用,使淀粉颗粒内部的结晶结构更完美,提高SDS含量,降低淀粉的消化性。湿热处理主要研究温度、水分含量和时间对SDS形成的影响。淀粉经过湿热处理后,消化性降低,当水分含量35%,温度120℃,时间为10h,SDS含量达9.25%。湿热处理对淀粉颗粒形貌影响不大,与原淀粉相比湿热处理淀粉膨胀度变小,糊粘度下降,起糊温度升高,糊化困难。湿热处理后To、Tp、Tc均上升,淀粉的晶型没有改变。
通过系统研究三种制备方法对淀粉性质、SDS含量和淀粉消化性的影响,认为普鲁兰酶脱支重结晶处理淀粉得到的SDS含量最高,是一种有潜力的制备SDS的方法。
Slowly digestible starches were defined as starches which were digested completely in small intestine of human, between 20 to 120 minutes, but the speed was slow. At present people prepared SDS mainly by enzyme, physical and chemical methods. This paper used waxy corn starch as material systemly studied to prepare SDS by debranching enzyme and recrystallization, octenyl succinic anhydride modifying, and hydrothermal treatment, then researched properties and mechanism of SDS.
Firstly, SDS was prepared by Pullulanase debranching then recrystaled. The effects of amount of Pullulanase, debranched time and recrystallization time on SDS content were studied. When concentration of Pullulanase was 20ASPU/g, debranched time was 6 hour and storaged 3 days at 4℃, content of SDS was 21.26%. The properties of SDS were determined by Scanning Electron Microscopy (SEM), x-ray dirffaction and Differential Scanning Calorimeter (DSC). Results showed that starch granule appearance changed remarkly and structure disappeared. Compared with native starch, crystal form of starch changed from A to B type, besides, DSC determination showed that To、Tp、Tc all increased,△H decreased remarkly, and these change had good relation with SDS content.
Secondly, SDS was prepared by octenyl succinic anhydride modifying. Researches showed that introduced big chemical group in favour of SDS formation by hindering enzymolysis, in addition, SDS content increased and digestibility reduced constantly as the degree of substitution improved. Compared with native starch, these modified starches had low pasting temperature, high peak viscosity, solubility and degree of swelling improved a lot. Besides, thermal parameters such as To、Tp、Tc and△H all reduced. Esterified starches still maintained A type crystal structure.
Thirdly, SDS was prepared by two kinds of hydrothermal treatment such as Annealing and Heat-Moisture Treatment (HMT). The effects of temperature, moisture and time on SDS content by annealing were investigated, and concluded that SDS content reach up to 8.35% when moisture was 60%, temperature 55℃and action time was 36 hours. Annealing changed starches’properties obviously, improved SDS content and reduced digestibility because of long time hydrothermal treatment. As far as HMT was concerned, the effect of treatment temperature, moisture and time on SDS content were also studied, when moisture was 35%, temperature 120℃and treated time was 10 hours, SDS got 9.25% maximum, reduce digestibility remarkly by generating SDS and Resistant Starches. Compared with native starch, HMT made swelling power, viscosity reduce, pasting temperature, To、Tp and Tc increase, but didn’t change crystal structure.
In conclution, by studying these three kinds of preparing methods on SDS content and starch digestibility. Considered that method of enzyme-debranching and recrystallization could achieve a good deal of SDS, which was very potential for SDS preparation.
引文
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[2]Subramony N, Moorthy. Physicochemical and Functional Properties of Tropical Tuber Starches: A Review[J].Starch,2002,54:559–592.
[3]Eerlingen R C, Jacobs H, Delcour J A .Enzyme-resistant starch.Effect of retrogradation of waxy maize starch on enzyme susceptibility[J].Cereal Chemistry, 1994, 71: 351-355.
[4]Fredrikssona.The influence of amylose and amylopectin characteristics on gelatinization and retrogradation properties of different starches[J].Carbohydrate Polymer,1998,35:119–134.
[5]Lovedeep K, Jaspreet S.Effect of cross-linking on some properties of potato starches[J].Science of Food and Agriculture,2006,86:1945–1954.
[6]Kawaljit S.Some properties of corn starches II: Physicochemical, gelatinization , retrogradation, pasting and gel textural properties[J].Food Chemistry,2007,101: 1499–1507.
[7]A.A.Karim.Methods for the study of starch retrogradation[J].Food Chemistry,2000, 71:9–36.
[8]Englyst, Kingman S M,ea tl.Classification and measurement of nutritionally important starch fractions[J].European Journal of Clinical Nutrition,1992,46,33-50.
[9]Alessandra S,Levitt MT.Measurement of starch absorption in human[J].Can J Pysiol Pharmacol,1991,69:108-112.
[10]Wolever T M S.Small intetinal effects of starchy foods[J].Canadian Journal of Physiology and Pharmacology,1991,69:93-99.
[11]Quezada-Calvillo R, Robayo-Torres C C,Ao Z,et al.Lumenal substrate“brake”on mucosal maltase-glucoamylase activity regulates total rate of starch digestion to glucose[J].Journal of Pediatric Gastroenterology and Nutrition,2007,45:32-43.
[12]Quezada-Calvillo R, Robayo-Torres C, Opekun A R, etal.Contributions of mucosal maltase glucoamylase activities to mouse small intestinal starch glucogenesis [J].Journal of Nutrition,2007,137:1725-1733.
[13]Brand J C, Nicholson P L,Thorburn A W.Food processing and the glycemic index[J].American Journal of Clinical Nutrition,1985,42:1192-1196.
[14]Bjorck I,Granfeldt Y,Liljeberg H,et al.Food properties affecting the digestion and absorption of carbohydrates[J].American Journal of Clinical Nutrition,1994,59:699S -705S.
[15]Bjorck I, Liljeberg H.Low glycaemic-index food[J].British Journal of Nutrition, 2000,83:149S-155S.
[16]Ludwig D S.The glycemic index:physiological mechanisms relating toobesity,diabetes,and cardiovascular disease[J].Journal of the American Medical Association,2002,287:2414-2423.
[17]Jenkins D J A, Kendall C W C, Augustin L S A, et al.Glycemic index:overview of implications in health and disease[J].American Journal of Clinical Nutrition, 2002, 76:266S-273S.
[18]Augustin L S, Franceschi S, Jenkins D J A, et al.Glycemic index in chronic disease:a review[J].European Journal of Clinical Nutrition,2002,56:1049-1071.
[19]Pi-Sunyer F X.Glycemic index and disease[J].American Journal of Clinical Nutrition,2002,76:290S-298S.
[20]Livesey G.Low-glycaemic diets and health:implications for obesity[J].proceeding of the Nutrition Society,2005,64:105-113.
[21]Ludwig D.S.The Glycemic Index: Physiological mechanisms relating to obesity, diabetes, and cardiovascular disease[J].Journal ofthe American Medical Association, 2002,287:2414-2423.
[22]Salmerón J,Ascherio A,Rimm E B,et al.Dietary fibre,glycemic load and risk of NIDDM in men[J].Diabetes Care,1997,20:545-550.
[23]Salmerón J, Manson J E, Stampfer M J, et al.Dietary fiber,glycemic load,and risk of non-insulin-dependent diabetes mellitus in women[J].Journal of the American Medical Association,1997,277:472-477.
[24]Jenkins D J.Glycemic index: overview of implications in health and disease[J]. American Journal of Clinical Nutrition,2002,76:266-273.
[25] Ells L J, Seal C J.Postprandial glycaemic, lipaemic and haemostatic responses to ingestion of rapidly and slowly digested starches in healthy young women[J].British Journal of Nutrition, 2005,94:948-955.
[26]Benton D, Nabb S. Carbohydrate, memory and mood [J].Nutrition Reviews, 2003,11:61-67.
[27]Campfield L A,Smith F J .Blood glucose dynamics andcontrol of meal initiation: a pattern detection and recognition theory[J].Physiological Reviews,2003,83:25-58.
[28]Leathwood P,Pollet P.Effects of slow release carbohydratesin the form of bean flakes on the evolution of hunger and satiety in man[J].1988,10:1-11.
[29]Brand-Miller J C, Holt S H A, Pawlak D B, et al.Glycemic index and obesity[J]. American Journal of Clinical Nutrition,2002,76:281S-285S.
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