肉桂酸基油脂凝胶的制备及其流变特性和结晶特性分析
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摘要
选择米糠油为溶剂体系,肉桂酸作为凝胶剂制备油脂凝胶,借助流变仪、X-射线衍射仪、荧光显微镜研究其流变特性及结晶特性。结果表明:米糠油凝胶的持油性和熔点随肉桂酸添加量的增加逐渐增加,当肉桂酸添加量超过10%,油脂凝胶的持油性和熔点增加不显著(P>0.05);米糠油凝胶的持油性随加热温度升高迅速上升,在85℃时升高至93.62%,此时的凝胶熔点也相对较高;当冷却温度从0℃升高至5℃时,凝胶的持油性和熔点相对较高,当冷却温度进一步升高,凝胶的持油性和熔点显著下降至93%(P<0.05)。通过对肉桂酸添加量10%、加热温度85℃、冷却温度5℃形成的油脂凝胶进行流变学特性分析,发现该油脂凝胶呈现假塑性流体状态,样品的表观黏度-剪切速率的关系符合幂律方程关系;并且在频率扫描范围内,油脂凝胶体系的储能模量(G’)明显大于损耗模量(G"),样品形成较为紧密的凝胶结构;通过凝胶结晶特性分析发现,米糠油凝胶中的结晶结构细小,分布均匀,存在同质多晶现象,主要含有β和β′2种晶体类型。
Cinnamic acid based rice bran oil organogel, prepared with rice bran oil as solvent and cinnamic acid as gelling agent, was characterized by X-ray diffraction(XRD), fluorescence microscope and rheometer for the analysis of rheological behavior and morphological structure. The results showed that the oil binding capacity and melting point gradually increased with cinnamic acid concentration up to 10%, and then did not significantly increase at higher cinnamic acid concentrations(P > 0.05); the oil binding capacity rapidly increased to 93.62% with temperature up to 85 ℃, and the melting point also reached a high level. The two parameters remain at a high level with increasing cooling temperature from 0 to 5 ℃, and then significantly decreased to 93% at higher cooling temperatures(P < 0.05). Rheological analysis showed that the organogel with 10% of cinnamic acid formed by heating at 85 ℃ and cooling at 5 ℃ was a pseudoplastic fluid and that the relationship between apparent viscosity and shear rate was fitted with the power law equation. Moreover, in the experimental range of frequency sweeping, the storage modulus(G′) was obviously higher than the loss modulus(G′′), indicating that the organogel had a compact structure. Under the microscope, tiny and evenly distributed crystal structures with polymorphism were observed and the main crystal structure types were β and β'.
Cinnamic acid based rice bran oil organogel, prepared with rice bran oil as solvent and cinnamic acid as gelling agent, was characterized by X-ray diffraction(XRD), fluorescence microscope and rheometer for the analysis of rheological behavior and morphological structure. The results showed that the oil binding capacity and melting point gradually increased with cinnamic acid concentration up to 10%, and then did not significantly increase at higher cinnamic acid concentrations(P > 0.05); the oil binding capacity rapidly increased to 93.62% with temperature up to 85 ℃, and the melting point also reached a high level. The two parameters remain at a high level with increasing cooling temperature from 0 to 5 ℃, and then significantly decreased to 93% at higher cooling temperatures(P < 0.05). Rheological analysis showed that the organogel with 10% of cinnamic acid formed by heating at 85 ℃ and cooling at 5 ℃ was a pseudoplastic fluid and that the relationship between apparent viscosity and shear rate was fitted with the power law equation. Moreover, in the experimental range of frequency sweeping, the storage modulus(G′) was obviously higher than the loss modulus(G′′), indicating that the organogel had a compact structure. Under the microscope, tiny and evenly distributed crystal structures with polymorphism were observed and the main crystal structure types were β and β'.
引文
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[22]杨丽君,孟宗,李进伟,等.分子蒸馏单甘酯含量对花生油基有机凝胶油性质的影响[J].中国油脂,2014,39(4):54-58.
[23]李满香,谢仕潮,张虹,等.机械搅拌对凝胶状油脂质构、流变及微观形态的影响[J].食品与生物技术学报,2013,32(4):393-398.DOI:10.3969/j.issn.1673-1689.2013.04.010.
[24]韩立娟.超分子油脂凝胶微观结构衍变与宏观性能变化的关系研究[D].广州:华南理工大学,2014:48-52.
[25]HAN L L,LI L,LI B,et al.Structure and physical properties of organogels developed by sitosterol and lecithin with sunflower oil[J].Journal of the American Oil Chemists’Society,2014,91(10):1783-1792.DOI:10.1007/s11746-014-2526-y.
[26]DICKINSON E,YAMAMOTO Y.Rheology of milk protein gels and protein-stabilized emulsion gels cross-linked with transglutaminase[J].Journal of Agricultural and Food Chemistry,1996,44:1371-1377.DOI:10.1021/jf950705y.
[27]LI X,SALEH A S M,WANG P,et al.Characterization of organogel prepared from rice bran oil with cinnamic acid[J].Food Biophysics,2017,12(3):1-9.DOI:10.1007/s11483-017-9491-6.
[28]朱小勇,孟宗,李进伟,等.凝胶剂种类对凝胶油物性及结晶形态的影响[J].中国粮油学报,2013,28(10):37-43.
[29]苏良瑶.振动剪切作用下聚合物及其复合材料的成型与性能研究[D].杭州:浙江大学,2015:12-15.
[30]HIGAKI K,SASAKURA Y,KOYANO T,et al.Physical analyses of gel-like behavior of binary mixtures of high-and low-melting fats[J].Journal of the American Oil Chemists’Society,2003,80(3):263-270.DOI:10.1007/s11746-003-0687-z.
[31]OJIJO N K O,NEEMAN I,EGER S.Effects of monoglyceride content,cooling rate and shear on the rheological properties of olive oil/monoglyceride gel networks[J].Journal of the Science of Food and Agriculture,2004,84:1585-1593.DOI:10.1002/jsfa.1831.
[32]钟金锋,覃小丽,刘雄.凝胶油及其在食品工业中的应用研究进展[J].食品科学,2015,36(3):272-279.DOI:10.7506/spkx1002-6630-201503051.
[2]DASSANAYAKE L S K,KODALI D R,UENO S.Formation of oleogels based on edible lipid materials[J].Current Opinion in Colloid&Interface Science,2011,16(5):432-439.DOI:10.1016/j.cocis.2011.05.005.
[3]MARANGONI A G,GARTI N.Edible oleogels:structure and health implications[M].Grasas Y Aceites:2011.
[4]JANG A,BAE W,HWANG H S,et al.Evaluation of canola oil oleogels with candelilla wax as an alternative to shortening in baked goods[J].Food Chemistry,2015,187:525-529.DOI:10.1016/j.foodchem.2015.0.4.110.
[5]HWANG H S,SINGH M,BAKOTA E L,et al.Margarine from organogels of plant wax and soy bean oil[J].Journal of the American Oil Chemists’Society,2013,90(11):1705-1712.DOI:10.1007/s11746-013-2315-z.
[6]ZETZL A K,MARANGONI A G,BARBUT S.Mechanical properties of ethylcellulose oleogels and their potential for saturated fat reduction in frankfurters[J].Food&Function,2012,3(3):327-337.DOI:10.1039/c2fo10202a.
[7]窦晓秋,张荻,冯传良.低分子量凝胶的研究进展及展望[J].科学技术与工程,2011,11(2):286-295.DOI:10.3969/j.issn.1671-1815.2011.02.014.
[8]刘宏,刘慧敏,冯国霞,等.植物甾醇+γ-谷维素型凝胶油的制备及其影响因素的研究[J].中国油脂,2015,40(6):66-71.DOI:10.3969/j.issn.1003-7969.2015.06.017.
[9]BALASUBRAMANIAN R,SUGHIR A A,DAMODAR G.Oleogel:a promising base for transdermal formulations[J].Asian Journal of Pharmaceutics,2012,6(1):1-9.DOI:10.4103/0973-8398.100118.
[10]DE P,BALTAS M,BEDOS-BELVAL F.Cinnamic acid derivatives as anticancer agents:a review[J].Current Medicinal Chemistry,2011,18(11):1672-1703.DOI:10.2174/092986711795471347.
[11]KIM E O,MIN K J,KWON T K,et al.Anti-inflammatory activity of hydroxy-cinnamic acid derivatives isolated from cor bran in lipopolysaccharide-stimulated raw 264.7 macrophages[J].Food and Chemical Toxicology,2012,50(5):1309-1316.DOI:10.1016/j.fct.2012.02.011.
[12]冯慧,林月英.R P-H P L C法测定咽炎片中哈巴俄苷和肉桂酸的含量[J].天津药学,2010,22(3):10-12.DOI:10.3969/j.issn.1006-5687.2010.03.005.
[13]张艳荣,丁伟,王大为.功能性米糠油超临界流体萃取工艺的研究[J].食品科学,2009,30(18):155-158.DOI:10.3321/j.issn:1002-6630.2009.18.032.
[14]PIEVE S D,CALLIGARIS S,CO E,et al.Shear nanostructuring of monoglyceride organogels[J].Food Biophysics,2010,5(3):211-217.DOI:10.1007/s11483-010-9162-3.
[15]ROCHA J C B,LOPES J D,MASCARENHAS M C N,et al.Thermal and rheological properties of organogels formed by sugarcane or candelilla wax in soy bean oil[J].Food Research International,2013,50(1):318-323.DOI:10.1016/j.foodres.2012.10.043.
[16]BLAKE A I,CO E D,MARANGONI A G.Structure and physical properties of plant wax crystal networks and their relationship to oil binding capacity[J].Journal of the American Oil Chemists’Society,2014,91(6):885-903.DOI:10.1007/s11746-014-2435-0.
[17]SATAPATHY D,BISWAS D,BEHERA B,et al.Sunflower oil based lecithin organogels as matrices for controlled drug delivery[J].Journal of Applied Polymer Science,2013,129(2):585-594 DOI:10.1002/app.38498.
[18]殷俊俊,马传国,王伟,等.利用γ-谷维素与β-谷甾醇制备葵花油凝胶研究[J].粮食与油脂,2015(1):39-42.DOI:10.3969/j.issn.1008-9578.2015.01.010.
[19]BOT A,GILBERT E P,BOUWMAN W G,et al.Elucidation of density profile of self-assembled sitosterol+oryzanol tubules with small-angle neutron scattering[J].Faraday Discussions,2012,158:223-238.DOI:10.1039/c2fd20020a.
[20]HWANG H S,KIM S,SINGH M,et al.Organogel formation of soybean oil with waxes[J].Journal of the American Oil Chemists’Society,2012,89(4):639-647.DOI:10.1007/s11746-011-1953-2.
[21]季文琴,王宝华,孟庆卿,等.肉桂酸在有机溶剂中溶解度的测定与关联[J].北京化工大学学报(自然科学版),2016,43(6):29-35.DOI:10.13543/j.bhxbzr.2016.06.005.
[22]杨丽君,孟宗,李进伟,等.分子蒸馏单甘酯含量对花生油基有机凝胶油性质的影响[J].中国油脂,2014,39(4):54-58.
[23]李满香,谢仕潮,张虹,等.机械搅拌对凝胶状油脂质构、流变及微观形态的影响[J].食品与生物技术学报,2013,32(4):393-398.DOI:10.3969/j.issn.1673-1689.2013.04.010.
[24]韩立娟.超分子油脂凝胶微观结构衍变与宏观性能变化的关系研究[D].广州:华南理工大学,2014:48-52.
[25]HAN L L,LI L,LI B,et al.Structure and physical properties of organogels developed by sitosterol and lecithin with sunflower oil[J].Journal of the American Oil Chemists’Society,2014,91(10):1783-1792.DOI:10.1007/s11746-014-2526-y.
[26]DICKINSON E,YAMAMOTO Y.Rheology of milk protein gels and protein-stabilized emulsion gels cross-linked with transglutaminase[J].Journal of Agricultural and Food Chemistry,1996,44:1371-1377.DOI:10.1021/jf950705y.
[27]LI X,SALEH A S M,WANG P,et al.Characterization of organogel prepared from rice bran oil with cinnamic acid[J].Food Biophysics,2017,12(3):1-9.DOI:10.1007/s11483-017-9491-6.
[28]朱小勇,孟宗,李进伟,等.凝胶剂种类对凝胶油物性及结晶形态的影响[J].中国粮油学报,2013,28(10):37-43.
[29]苏良瑶.振动剪切作用下聚合物及其复合材料的成型与性能研究[D].杭州:浙江大学,2015:12-15.
[30]HIGAKI K,SASAKURA Y,KOYANO T,et al.Physical analyses of gel-like behavior of binary mixtures of high-and low-melting fats[J].Journal of the American Oil Chemists’Society,2003,80(3):263-270.DOI:10.1007/s11746-003-0687-z.
[31]OJIJO N K O,NEEMAN I,EGER S.Effects of monoglyceride content,cooling rate and shear on the rheological properties of olive oil/monoglyceride gel networks[J].Journal of the Science of Food and Agriculture,2004,84:1585-1593.DOI:10.1002/jsfa.1831.
[32]钟金锋,覃小丽,刘雄.凝胶油及其在食品工业中的应用研究进展[J].食品科学,2015,36(3):272-279.DOI:10.7506/spkx1002-6630-201503051.