甘薯交联淀粉的制备与结构表征

以三偏磷酸钠为交联剂,水分散法制备了甘薯交联淀粉,应用红外光谱、X射线衍射、扫描电镜和偏光显微镜等分析测试方法,观察和研究了不同取代度甘薯交联淀粉的颗粒形貌及其结晶结构。结果表明,产物取代度随交联反应时间的延长而增大;交联反应主要发生在淀粉分子的无定形区,在结晶区也有一定程度的反应;随着取代度的增大,淀粉颗粒表面发生了明显变化,同时出现了大小球体相分离的现象,说明了交联反应主要发生在甘薯淀粉颗粒的表面和大小球体间的联接处;交联淀粉的偏光十字清晰易见;1016.28cm-1的吸收峰强度加强,证实在淀粉中引入了磷酸根基团。     

羟丙基淀粉颗粒形貌和结晶结构的研究

本文应用扫描电镜、X-光衍射和偏光显微等现代分析技术，观察和研究了不同取代度羟丙基淀粉和原淀粉的颗粒形貌及其结晶结构。结果表明：淀粉羟丙基化反应首先发生在淀粉颗粒中结构较薄弱的非结晶区。随着取代度增大，淀粉颗粒表面发生凹凸不平变化，出现洞穴和裂痕，使淀粉易于糊化，糊化温度降低。     

马铃薯辛烯基琥珀酸淀粉酯颗粒及结晶结构研究

利用偏光显微镜直观手段和X–衍射分析手段对马铃薯淀粉及其不同取代度辛烯基琥珀酸淀粉酯颗粒和结晶结构进行研究;结果表明,酯化后淀粉颗粒完整性遭到轻微破坏,部分淀粉颗粒偏光十字消失,结晶度有所下降,但淀粉晶型并没改变。     

三偏磷酸钠高交联马铃薯淀粉非糊化特征研究

研究了以三偏磷酸钠为交联剂制备非糊化的高交联马铃薯淀粉的方法;测定了反应的取代度和布拉班德粘度曲线,提出高交联马铃薯淀粉与原淀粉颗粒不同,在沸水中只发生轻微溶胀,呈非糊化颗粒态。     

三氯氧磷交联淀粉生物降解过程中形貌和结晶结构的变化

利用扫描电子显微技术和多功能偏光显微技术系统研究三氯氧磷交联淀粉在生物降解过程中的颗粒形貌和结晶结构变化情况.结果表明：随着交联度的增大,颗粒被微生物破坏的程度变小.经三氯氧磷高交联后的木薯淀粉在微生物降解过程中颗粒的偏光十字变化不明显,表明一定程度的三氯氧磷交联会抑制微生物对淀粉颗粒的作用.     

超声波作用对木薯淀粉化学反应性能的影响

淀粉颗粒内部具有结晶区和非结晶区,淀粉的变性化学反应主要发生在非结晶区。实验表明,超声波作用的木薯淀粉颗粒基本保持着原木薯淀粉的颗粒形状,而木薯淀粉颗粒的偏光十字特征减弱或消失;超声波作用没有破坏木薯淀粉分子的原有的结构,没有新的化合物产生,经超声波作用后的木薯淀粉的红外结晶指数下降,木薯淀粉颗粒表面不再圆滑平整,说明超声作用破坏了木薯淀粉颗粒表层结晶结构。超声波作用后的木薯淀粉与原木薯淀粉分别合成羟丙基淀粉,羟丙基淀粉的取代度分别为0.1895与0.0725,说明经超声波作用后的木薯淀粉的反应性能增强,因为超声波作用后的木薯淀粉颗粒结晶结构被破坏,反应试剂更容易进入淀粉颗粒内部进行反应,反应性能得到了提高。     

乌冬面专用变性淀粉及其结构表征

采用交联―酯化―预糊化复合变性制备乌冬面专用改性淀粉,并与木薯原淀粉、交联淀粉及交联―酯化淀粉进行比较。结果表明,交联淀粉偏光显微及颗粒形貌没发生明显变化,交联变性并未破坏淀粉结晶结构;交联―酯化淀粉颗粒出现粘连和聚集现象,部分颗粒表面出现凹陷和裂纹现象;红外光谱表明,交联―酯化―预糊化复合变性淀粉在1 728 cm–1、1 247 cm–1附近出现新的吸收峰,分子内引入乙酰基团,X–射线衍射光谱显示,交联―酯化―预糊化复合变性淀粉在5.6°和22°处衍射峰强度减弱,A型特征峰加强,结晶类型由"C"型向"A"型转变;交联―酯化淀粉经预糊化处理后,淀粉颗粒膨胀破裂,结晶结构受到彻底破坏,淀粉偏光十字消失,但预糊化处理未破坏淀粉分子化学键。     

高交联马铃薯淀粉非糊化特性研究

研究了以三氯氧磷为交联剂制备非糊化的高交联马铃薯淀粉的方法，测定了反应的取代度和布拉班德粘度曲线，研究了在沸水中受热后非糊化淀粉的颗粒形貌及粒度分布等特性。提出高交联非糊化马铃薯淀粉存在着不同于原淀粉颗粒的沸水中只发生轻度有限溶胀的非糊化颗粒态。     

不同取代度交联紫薯淀粉性能与表征

为探究不同取代度对交联淀粉的影响,本文以紫薯淀粉为原料,以三偏磷酸钠和三聚磷酸钠混合物为交联剂,制备了交联紫薯淀粉,并对不同取代度(0.0053～0.0212)交联紫薯淀粉进行了性能测定及表征。结果表明:随着取代度的增加,交联紫薯淀粉的透明度和溶解度上升,膨胀度下降,冻融稳定性增加。紫薯淀粉颗粒的表面完整光滑,而交联紫薯淀粉颗粒则呈现剥离状外观,颗粒之间作用力增强,黏连聚集现象明显。所有样品的结晶类型均为C型结晶,交联紫薯淀粉平均粒径与紫薯淀粉相比差异不显著,但结晶度则随取代度升高而逐渐下降,且交联紫薯淀粉所带负电荷也随取代度升高而逐渐增多。因此,与紫薯淀粉相比,交联紫薯淀粉的多种性能均有所提升,且与取代度关系密切,这为紫薯资源的深入开发提供了理论依据。     

氧化交联淀粉取代丁苯胶乳对涂布纸性能的影响

以马铃薯淀粉为原料,在氧化剂次氯酸钠、交联剂六偏磷酸钠和助剂纳米纤维素(NCC)的作用下制备氧化交联马铃薯淀粉。并以此改性淀粉取代部分丁苯胶乳,探究其对涂料和涂布铜版纸性能的影响。研究表明:在马铃薯淀粉的氧化交联反应中,加入一定量的NCC能提高氧化交联马铃薯淀粉的羧基含量和交联度;涂料的黏度都随改性淀粉取代丁苯胶乳份数的增加而增加,并且当改性淀粉取代丁苯胶乳的份数不超过3份时,对涂料的黏度影响不大;含有一定量NCC的改性淀粉取代部分丁苯胶乳后的涂布纸,平滑度、阻隔空气能力、表面强度和抗水性都优于不含NCC的改性淀粉的涂布纸。并且当含有一定量NCC的改性淀粉取代丁苯胶乳的份数不超过3份时,涂布纸的白度、平滑度、阻隔空气能力和表面强度都优于全丁苯胶乳涂料的涂布纸。     

Preparation of highly substituted carboxymethyl starch using a twin‐screw extruder

Carboxymethyl starch was prepared by reacting corn starch with sodium mono chloro acetate (SMCA) in a Brabender TSE‐20 co‐rotating twin screw extruder. The effects of the SMCA/starch ratio (theoretical degrees of substitutions 2.73, 3.62, and 4.53), aqueous ethanol/(starch + SMCA) ratio (0.13 and 0.25) and the screw configuration (0, 1, and 2 kneading blocks) on the degree of substitution (DS) and reaction efficiency were studied. A 3 × 2 factorial design with 3 levels of the starch/SMCA ratio and 2 levels of the aqueous ethanol/(starch + SMCA) ratio were used. This 3 × 2 factorial design was blocked, with the screw configuration as the blocking variable. The effects of the SMCA/starch ratio and the screw configuration were found to be significant. The carboxymethylated starches were characterized using FTIR, SEM, and XRD. The microstructure of the carboxymethylated starches, studied using SEM, revealed that the integrity of the starch granules was partially preserved at low aqueous ethanol levels when no kneading block was used. However, for all other reaction conditions either granule agglomeration or fusion was observed. XRD analysis indicated substantial loss of crystallinity in the carboxymethylated starches, irrespective of the damage to the granule structure. The highest DS and the highest reaction efficiency obtained were 1.54 and 0.42, respectively.     

木薯羧甲基淀粉的机械活化固相化学法制备、表征及其特性

以木薯淀粉为原料,氯乙酸钠为醚化剂,氢氧化钠为催化剂,采用机械活化固相化学反应法制备羧甲基淀粉。以取代度为评价指标,通过单因素和正交试验设计优化确定最佳制备工艺,采用傅里叶红外光谱（Fourier transform infrared spectroscopy,FTIR）、X-射线衍射（x-ray diffraction,XRD）、扫描电镜（scanning electron microscope,SEM）对羧甲基淀粉的结构进行表征,并考察羧甲基淀粉的理化特性。结果表明,最佳工艺参数为淀粉与氯乙酸钠物质的量比1∶1、反应温度50?℃、反应时间1.5?h、氢氧化钠溶液质量分数18.8%、搅拌速率380?r/min、球磨介质堆体积500?mL,在此条件下制备的羧甲基淀粉取代度为0.540?1。FTIR、XRD、SEM检测进一步证实木薯淀粉发生了羧甲基化反应。理化特性结果显示,羧甲基淀粉的黏度升高,溶解度增大,吸水性、保水性、冻融稳定性、抗酸碱性、抗酶解性等均得到较好的提高。     

羟丁基化水平对玉米淀粉理化性质的影响

以玉米淀粉为原料,1,2-环氧丁烷为醚化剂,氢氧化钠为催化剂,乙醇为分散剂,制备出不同取代度的羟丁基淀粉。采用傅里叶变换红外仪、X射线衍衍射仪和扫描电镜等对不同取代度的羟丁基淀粉的微观结构进行表征。红外分析表明羟丁基淀粉在1371cm-1出现羟丁基的吸收峰,证明已经接上了羟丁基基团。X射线衍射分析羟丁基淀粉仍属于A型衍射图,证实了该反应主要发生在无定形区。通过扫描电子显微镜分析变性前后的表面形貌变化,表明该反应发生在淀粉颗粒表面。布拉班德粘度仪测试结果表明,淀粉糊化温度降低,回复值降低,糊峰值黏度升高,且随着取代度的提高,变化越明显,当取代度达到一定程度时,羟丁基淀粉冷水可溶。随着羟丁基取代度的增大,淀粉糊的透明度及冻融稳定性都有显著的提高。     

Synthesis of high fatty acid starch esters with 1‐butyl‐3‐methylimidazolium chloride as a reaction medium

In this work, high fatty acid esters of corn starch were synthesized by reacting the starch with fatty acid methyl ester using 1‐butyl‐3‐methylimidazolium chloride (BMIMCl) ionic liquid (IL) as reaction media. The effect of reaction variables such as the catalyst amount, molar ratio of fatty acid methyl ester/anhydroglucose unit (AGU) in starch, pyridine/AGU molar ratio, reaction temperature, as well as reaction time on the degree of substitution (DS) of starch esters was investigated. The experimental results showed that the DS value of the obtained starch esters could be varied depending on the process conditions. In the optimum reaction condition, the achieved maximum DS of starch laurate and starch stearate was 0.37 and 0.28, respectively, at a reaction temperature of 110°C for starch laurate and 120°C for starch stearate for a reaction duration of 2 h. Furthermore, the starch esters were characterized by FTIR, SEM, and X‐ray diffractometry (XRD) techniques, respectively. Results from FT‐IR spectroscopy suggested that the hydroxyl groups in the starch molecules were converted into ester groups. SEM and XRD studies showed that the morphology and crystallinity of starch esters were disrupted largely in the IL medium under the reaction conditions.     

Homogeneous synthesis and characterization of starch acetates in ionic liquid without catalysts

Homogeneous modification of corn starch with acetic anhydride was performed in ionic liquids 1‐butyl‐3‐methylimidazolium chloride (BMIMCl) without catalysts. The results indicated that the pretreatment of starch, which starch was dissolved in BMIMCl at 105°C for 2 h before reaction, provided feasible reaction environment for starch functionalization. Optimum modification conditions for maximum degree of substitute (DS 2.11) were shown as following: acetic anhydride/anhydroglucose units (AGU) molar ratio 5:1, reaction temperature 105°C and reaction time 2 h. The pretence of acetyl groups in starch products was confirmed by FTIR and ¹H NMR spectroscopy. SEM and XRD data showed that the crystalline structure of native starch was disrupted and new structure was formed during the dissolution and modification processes. The higher DS due to acetylation had a beneficial effect on the thermal stability of samples.     

戊二酸蜡质玉米淀粉酯的制备及理化性质研究

以原蜡质玉米淀粉为原料,戊二酸酐为酯化剂,乙醇为反应溶剂制备戊二酸淀粉酯(EGAS)。采用傅里叶变换红外光谱（FT-IR）、扫描电子显微镜（SEM）、X射线衍射仪（XRD）及布拉班德粘度仪等对样品进行表征及理化性能分析。结果表明：FT-IR显示戊二酸淀粉酯在1730 cm-1处和1565 cm-1处出现了新的吸收峰,其中1730 cm-1处为C=O的伸缩振动吸收峰,1565 cm-1处为游离的-COO-的反对称伸缩振动吸收峰,表明了淀粉分子中成功接入了戊二酸基团;改性前后淀粉的表观形貌变化,证实了反应不仅发生在淀粉颗粒表面,也发生在淀粉颗粒内部;XRD分析显示改性后的淀粉仍属于A型结晶结构,表明了反应主要发生在无定形区;布拉班德粘度分析则表明了改性后的淀粉（DS=0.0450）峰值粘度提高了2.33倍;EGAS的冻融稳定性和抗剪切力均强于原淀粉,糊的透明度得到改善。     

The structure of C-type Rhizoma Dioscorea starch granule revealed by acid hydrolysis method

Scanning electron microscope (SEM), X-ray powder diffraction (XRD) and cross polarisation/magic-angle spinning (CP/MAS) ¹³C nuclear magic resonance (NMR) have been used for the structural characterisation of C-type starch granule during acid hydrolysis. SEM shows that the amorphous areas mainly locate the core part of C-type starch granules, while the crystalline areas mainly exist in the peripheral region of starch granules. XRD analysis reveals that the B-type polymorph present in the C-type starch granule are preferentially degraded or degraded faster than the A-type polymorph. NMR spectra confirm that the amorphous regions in the starch granules are firstly hydrolysed and could be hydrolysed completely as long as the hydrolysis time is sufficient. After 40 days of hydrolysis, the acid-modified starch shows typical A-type characteristics upon analysis of the XRD pattern or the ¹³C CP/MAS NMR spectra.     

Facile preparation of sago starch esters using full factorial design of experiment

A facile solvent‐free method to acetylate sago starch (Metroxylon sagu) is reported. Microwave (100 W) was used as the heating source and the heating time was varied from 2 to 10 min with the temperature of acetylation maintained at 100°C under continuous stirring. Using a 2⁴ full factorial design of experiment, it was found that the degree of substitution (DS) of acetylated sago starch was strongly affected by the ratio of starch to acylating reagents, the ratio of acetic anhydride to acetic acid as the acylating reagents, the concentration of iodine as catalyst and reaction time. The physicochemical characteristics of the acetylated sago starch were assessed based on the FTIR spectra, the XRD spectra, the water absorption index (WAI), and the water solubility index (WSI). SEM was used to study the surface morphology of the acetylated sago starch at different DS.     

Microwave assisted synthesis and characterization of Sago starch‐g‐acrylamide

In the present investigation, sago starch was modified through microwave assisted chemical synthesis using acrylamide as grafting monomer. Grafted copolymer was characterized by fourier transform infra red spectroscopy (FTIR), scanning electron microscopy (SEM), X‐ray powder diffractometer (XRD) and thermo gravimetric analysis (TGA). Swelling study was also performed at various temperatures to access its suitability in diverse industrial application. The optimum reaction conditions were found as follows: starch, 1 g; acrylamide (AMD), 5 g; microwave power, 600 W, reaction time, 3 h. Grafting on the starch backbone confirmed by FTIR spectral analysis, while XRD confirmed formation of more crystalline structure after AMD grafting. TGA analysis showed formation of more thermostable copolymer after grafting, while swelling study proved its suitability for various industrial applications due to its extensive swelling at higher temperatures.