以慈姑淀粉为研究对象,利用H2O2作氧化剂,CuSO4作催化剂,采用湿法制备氧化慈姑淀粉,并探讨氧化前后淀粉的性质变化。利用单因素实验考察H2O2添加量、CuSO4添加量、反应pH 值、反应时间对氧化慈姑淀粉的影响,在单因素实验基础上,以淀粉羧基含量及透明度为响应值设计响应面实验,优化制备工艺,并对氧化前后的慈姑淀粉的性质进行测定。得到最佳氧化工艺:100 g淀粉乳溶液中(质量分数40%)加入31.6 mL H2O2,使pH 为8.35,CuSO4用量取干基的0.04%,45 ℃条件下反应4 h,所得氧化慈姑淀粉的羧基含量为0.355%,透明度为52.6%;氧化后慈姑淀粉的溶解度与膨润度随着温度的升高而逐渐升高,凝沉性优于慈姑淀粉,冻融稳定性变差,黏度降低,淀粉的糊化温度变低;颗粒破碎严重、形状增多;红外光谱中,在1 760~1 660 cm-1吸收峰型更尖且强,羰基振动增强;氧化后慈姑淀粉的X-衍射特征衍射峰变高,结晶度从44.80%升高至55.11%。综上,经过H2O2/CuSO4氧化的慈姑淀粉为高羧基含量、高透明度慈姑淀粉,同时氧化淀粉的理化特性、颗粒状态、晶体结构等均发生了变化,该研究为此条件下所得慈姑氧化淀粉的开发与利用提供理论基础。
In this paper, arrowhead starch was modified by wet oxidation with hydrogen peroxide (H2O2) as oxidant and copper sulfate (CuSO4) as the catalyst. And the properties of starch before and after oxidation were discussed. Single factor experiments were designed to investigate the effects of additive amount of H2O2, CuSO4, pH value and reaction time on the oxidation of arrowhead starch. Based on the single factor experiment, the carboxyl content and transparency of starch were taken as the response value to design the response surface experiment so as to optimize the preparation process, and the properties of arrowhead starch before and after oxidation were tested. The best oxidation process was obtained as follows: 31.6 ml of H2O2 was added into starch emulsion solution (100 g, 40%, w/w) to have pH at 8.35, the amount of CuSO4 was 0.04% of the dry basis, and the reaction time was 4 hours at 45 ℃. The carboxyl content of the oxidized arrowhead starch was 0.355%, and the transparency was 52.6%. The solubility and swelling degree of oxidized starch increased significantly with the increase of temperature. The coagulability of oxidized starch was better than before; the freeze-thaw stability was worse; the viscosity was lower, and the gelatinization temperature of starch became lower. The particles were broken greatly and the shape increased; in the infrared spectrum, the absorption peak of 1 760-1 660 cm-1 was sharper and stronger, and the carboxyl vibration was enhanced. The X-diffraction characteristic diffraction peak of oxidized starch became higher, and the crystallinity increased from 44.80% to 55.11%. In conclusion, the arrowhead starch oxidized by H2O2/CuSO4 has high carboxyl content and high transparency. At the same time, the physical and chemical properties, particle state and crystal structure change, which provides a theoretical basis for the development and utilization of the oxidized arrowhead starch.
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