疏水改性籽粒苋淀粉颗粒稳定的Pickering乳液

利用碱提法从籽粒苋种子中提取了籽粒苋淀粉(St)颗粒,使用辛烯基琥珀酸酐(OSA)对提取的淀粉颗粒进行疏水改性,得到了两亲性的辛烯基琥珀酸淀粉酯(OSA starch)颗粒。通过红外光谱(FTIR)及X射线衍射仪(XRD)对其结构进行了表征。随着改性淀粉颗粒取代度的增加,其疏水性增强。以液体石蜡作为油相,将改性淀粉颗粒作为单一的乳化剂应用于Pickering乳液的制备。当油水体积比为1∶1时,取代度为0.089的改性淀粉颗粒的质量分数为0.5%以上,即可得到优异稳定性的乳液。随着改性淀粉颗粒用量的增加,乳液液滴粒径变小,乳液稳定性增强。     

辛烯基琥珀酸淀粉钠的制备及其结构表征

研究了辛烯基琥珀酸淀粉钠(SSOS)的生产方法,并采用红外光谱仪对产品的结构进行了分析。实验结果表明,蜡质玉米淀粉经辛烯基琥珀酸酐(OSA)处理后,产品的取代度为0 017,反映在光谱图上1724cm-1和1565cm-1处产生了新的吸收峰,608cm-1处的吸收峰加强,这些都是OSA基团的特征峰。在制备低黏度SSOS时,α 淀粉酶作用酯化淀粉后产品的DE值(dextroseequivalent)为2 5～6 4,再经糖化酶作用后产品的DE值为14 5～37,可根据最终产品的DE值要求来确定酶的用量以及是否用糖化酶。     

低取代度碎米淀粉辛烯基琥珀酸酯的工艺分析

碎米淀粉与辛烯基琥珀酸酐酯化生成辛烯基琥珀酸淀粉酯,其是典型的慢消化淀粉,低取代度时可任意比例加入食品。试验分析反应时间、pH、温度、淀粉浓度及辛烯基琥珀酸酐加入量对酯化淀粉取代度的影响;从单因素及工业生产考虑,分别在反应时间3 h、pH 8. 5、反应温度35℃、淀粉乳浓度35%及辛烯基琥珀酸酐用量2%时,酯化取代度较为合适。     

超声作用下辛烯基琥珀酸淀粉酯合成工艺及反应机理研究

以木薯淀粉为原料,辛烯基琥珀酸酐为变性剂,采用湿法工艺,在超声作用下制备辛烯基琥珀酸淀粉酯.用单因素实验探索最佳制备工艺条件及酯化反应机理.结果表明,超声作用制备辛烯基琥珀酸淀粉酯的最佳工艺条件为：超声作用时间30 min,超声功率250 W,酯化pH 8.5,反应温度35℃,在最佳工艺条件下制备所得辛烯基琥珀酸淀粉酯取代度达0.0181,比未施加超声作用所制得的产品取代度提高了28.4％.超声波强化淀粉变性反应机理是超声波的空化效应对木薯淀粉的颗粒结构有一定影响,使淀粉颗粒表面变粗糙,增加了反应物之间的接触面积,强化了酯化反应的发生.     

酯化改性多孔淀粉的制备研究

采用十二烯基琥珀酸酐对多孔淀粉进行酯化改性,探讨反应温度、反应时间和十二烯基琥珀酸酐用量对改性淀粉取代度的的影响,并采用傅立叶红外光谱仪对酯化多孔淀粉的结构进行表征。研究结果表明,当反应温度40℃、反应时间8h、十二烯基琥珀酸酐用量为多孔淀粉的6%时,酯化多孔淀粉的取代度最佳。     

非晶交联辛烯基琥珀酸淀粉酯的一步法合成及其性能

以非晶木薯淀粉(N-NS)为原料,三偏磷酸钠(STMP)和辛烯基琥珀酸酐(OSA)为变性剂,采用一步法合成非晶交联辛烯基琥珀酸淀粉酯(N-1-COSAS),测定产物的取代度、结合磷含量、透明度、表观黏度、特性黏度和蓝值,并与三步法合成的非晶交联辛烯基琥珀酸淀粉酯(N-3-COSAS)作对比。同时采用傅里叶红外光谱仪(FT-IR)、扫描电镜(SEM)、X射线衍射仪(XRD)和差示扫描量热仪(DSC)对产物的官能团、形貌、结晶结构和热稳定性进行表征。结果表明,N-1-COSAS的取代度、结合磷含量、特性黏度要比N-3-COSAS的大,糊化温度比N-3-COSAS的低;N-1-COSAS与N-3-COSAS在1600 cm–1附近都出现了辛烯基C=C特征吸收峰,表明酯化反应的发生;N-1-COSAS与N-3-COSAS的结晶度均比原淀粉低,峰的弥散程度与N-NS相似;N-1-COSAS与N-3-COSAS颗粒表面比N-NS更加粗糙,且这二者的热稳定性优于N-NS。     

高取代度辛烯基琥珀酸环糊精酯的制备及其性能研究

以辛烯基琥珀酸酐(OSA)与β-环糊精(β-CD)为原料,采用优化后的非均相反应制备高取代度辛烯基琥珀酸环糊精酯(OS-β-CD)。通过FT-IR分析改性前后样品特征峰的变化表明,成功合成出了辛烯基琥珀酸环糊精酯。通过TGA分析发现,改性后样品的热稳定性有所降低,但耐热稳定性仍能满足其在多种领域中的应用。与β-环糊精相比,OS-β-CD在冷水中的溶解性能得到明显提高,OS-β-CD质量分数为15%时,溶液的透光率仍高达90%。随着分子链段中辛烯基琥珀酸阴离子基团引入量的增加,溶液的表面张力降低,最低可达44.09 mN/m,同时分子间静电排斥作用和支化度的提高抑制了OS-β-CD分子的重新排列,促进了酯化物溶液的耐冻融稳定性。     

离子液体介质中OSAS的制备与表征及乳化性质分析

以玉米淀粉（CS）为原料,辛烯基琥珀酸酐（OSA）为酯化剂,在无催化剂条件下,在1-烯丙基-3-甲基氯化咪唑离子液体（AMIMCl）介质中,通过均相酯化反应制备辛烯基琥珀酸淀粉酯（OSAS）。利用红外光谱（FTIR）、X射线衍射（XRD）、扫描电镜（SEM）、热重-红外联用仪（TGA-FTIR）、凝胶渗透色谱（GPC）和偏光显微镜（POM）对产物结构、热特性、相对分子质量及乳化性质进行分析。结果表明,制备OSAS的较佳工艺条件为：时间2h,温度90℃,淀粉质量分数6%,OSA与淀粉脱水葡萄糖单元（AGU）摩尔比可根据所需产品的取代度在0.03～0.24范围内选取。FTIR分析表明,CS已成功发生了酯化反应;XRD与SEM证明所得OSAS为无定形形态的细小颗粒聚结物;TGA-FTIR测试表明,在氮气环境中,OSAS中所接入的辛烯基琥珀酸酯基团能稳定至200℃;GPC与POM证明AMIMCl介质中制备的OSAS是优良的大分子乳化剂。     

高取代度环烯基琥珀酸淀粉酯的合成研究

根据淀粉的结构和性质可以对其进行改性,从而改善淀粉自身的一些缺陷．扩大它的应用范围。琥珀酸淀粉酯是一种重要的变性淀粉,是由烯基琥珀酸酐和淀粉通过酯化反应制得的,其物理化学特性与淀粉相比发生了很大变化,在工业领域得以广泛应用。常用的淀粉酯有辛烯基琥珀酸淀粉酯SSOS和十二烯基琥珀酸淀粉酯SSDS。 合成烯基琥珀酸酐所用的原料一般通过α-烯烃双键异构化的方法获得。由于核算关键异构化产物的平衡受热力学控制,难以在一次平衡中获得α-烯质量分数低于5％的产物。因此必须采用“全异构化”工艺,但是经济成本过高．实施起来比较困难。现以含有共轭双键的山梨酸为原料,以顺丁烯二酸酐（马来酸酐）为亲二烯加成试剂,发生D-A反应制得环烯基琥珀酸酐。这两种原料价格适当,分布合理,是比较理想的原料。     

有机相法合成辛烯基琥珀酸淀粉酯

变性淀粉工业是国内具有广阔的市场前景的工业之一。辛烯基琥珀酸淀粉酯是种非常重要的亲油脂变性淀粉,乳化稳定,效果优良,对人体无毒副作用,作为一种新的食品添加剂,成为国际上通用的安全添加剂,在各种行业都有广泛的应用。本研究从反应机理出发,以丙酮为分散相,进行反应。探索了多种催化剂,寻找最佳催化剂;通过实验确定以磷酸钠作为催化剂。以此基础上,探索不同浓度的辛烯基琥珀酸酐(OSA)对反应取代度的影响,寻找合适的反应条件。最适宜的反应条件为:OSA反应浓度为0.6 mol/L,需要的丙酮体积为150 mL,磷酸钠质量为7 g,加热温度为40℃,加热时间为4 h。     

The effect of temperature on the observed flow-induced structure in semidilute solutions of gently solubilized starches

The effect of temperature on the unexpected shear-thickening behavior exhibited by semidilute solutions of waxy maize starch during a repeated shear-loop experiment was evaluated. Shear-thickening behavior, characterized using power law models, was observed for waxy maize starch, but not for normal maize starch at the same concentration. The shear-thickening region was observed for waxy maize starch at temperatures ranging from 25°C to 80°C and shear rates from 2–100 s^?1 during the initial part of the shear-loop experiment. For waxy maize starch, the power law exponent, n, was found to be 0.539 ± 0.017 in the shear-thinning region. For normal maize starch, the value of n was found to be equal to 0.751 ± 0.015 and only shear-thinning behavior was observed. The values of n for both waxy maize and normal maize starch were found to be temperature independent within the precision of the experimental measurements. The differences in n indicate the differences in the conformational dynamics of waxy maize and normal maize starches in solution.     

阳离子改性淀粉絮凝剂的制备及应用

以糯玉米淀粉为原料,3-氯-2-羟丙基三甲基氯化铵为阳离子醚化剂,采用预干燥干法制备高取代度季铵型阳离子淀粉絮凝剂.考察了醚化剂用量、氢氧化钠与醚化剂摩尔比、反应温度及反应时间对取代度的影响,优化出制备高取代度阳离子淀粉的最佳工艺条件为:醚化剂的加入量为绝干淀粉量的52.5%,氢氧化钠与醚化剂摩尔比为1.2,反应温度80℃,反应时间5 h.将阳离子淀粉对玫瑰花色素酒精废液进行絮凝脱色性能测定,结果表明当阳离子淀粉量浓度为1250 mg·L-1、取代度为0.3342时,脱色率达78.42%.     

Effects of drying process for amorphous waxy maize starch on theophylline release from starch‐based tablets

Physical properties and theophylline‐release profiles of compressed tablets prepared with amorphous waxy maize starches dried using different methods were examined. A gelatinized waxy maize starch paste (10% solids in water) was either freeze‐dried or oven‐dried (40 or 105°C) until the moisture content reached to <5%. To form the tablets, the dried amorphous starch powders, either with or without theophylline (3 : 10, w/w), were remoistened to a water content of (17 ± 0.2)%, and compressed into tablets. The drying process applied to the amorphous starch powders affected both the compactness and swelling behavior of the tablets. Although no crystallinity was detected in all the starches tested, X‐ray diffraction patterns indicated that starch chains dried at the lower temperature (40°C) are allowed more time to re‐associate during the drying process than those dried at the higher temperature (105°C). The freeze‐dried starch powders formed tablets characterized by greater compactness and rigidity than was observed in the oven‐dried starch samples. The drug release of the tablets prepared with the starch dried at the higher temperature (105°C) occurred at a much slower rate than that of the tablets made with the starch dried at the lower temperature (40°C). The drug release characteristics of the freeze‐dried starch tablets were nearly identical to those of the tablets prepared with the starch dried at 105°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Thermoplastic starch blends with a poly(ethylene-co-vinyl alcohol): Processability and physical properties

We investigated the effect of poly(ethylene-co-vinyl alcohol) (EVOH) concentration on the processability and physical properties of thermoplastic starch plasticized with glycerine and water. Waxy maize starch (Amioca), native corn starch (Melogel), and a treated high amylose corn starch (Hylon VII) were employed to explore the effect of starch type on blend properties. All the starches exhibited similar changes in properties with increasing EVOH content. The minimum injection pressure required for filling a standard test specimen (a measure of processability) decreased with increasing EVOH concentration and provided an indication of improved processability. Blends with high amylose corn exhibited higher injection pressures than the corresponding waxy maize or native corn starch blends. The ductility of all the thermoplastic starches was significantly increased upon the addition of EVOH. The waxy maize blends were stiffer and the high amylose corn blends exhibited higher elongation at low EVOH concentrations, but all the starch/EVOH blends exhibited similar physical properties when the EVOH concentration was ≥ 50 wt%. An investigation of physical properties of this blend series after long term aging from 10% to 90% relative humidity is in progress. Future studies include rheology, electron microscopy, and thermal analysis to more fully elucidate phase behavior in these binary blends.     

Effect of enzymatic treatment of different starch sources on the in vitro rate and extent of starch digestion

Gelatinized wheat, potato and waxy maize starches were treated enzymatically in order to increase the degree of branching of the amylopectin fraction and thereby change the starch degradation profile towards a higher proportion of slowly digestible starch (SDS). The materials were characterized by single-pulse (1)H HR-MAS NMR spectroscopy and in vitro digestion profile according to the Englyst procedure. Using various concentrations and incubation times with branching enzyme (EC 2.4.1.18) without or with additional treatment with the hydrolytic enzymes; β-amylase (EC 3.2.1.2), α-glucosidase (EC 3.2.1.20), or amyloglucosidase (EC 3.2.1.3) the proportion of α-(1-6) linkages was increased by up to a factor of 4.1, 5 and 5.8 in waxy maize, wheat and potato starches, respectively. The proportion of SDS was significantly increased when using hydrolytic enzymes after treatment with branching enzyme but it was only for waxy maize that the proportion of α-(1-6) bonds and the in vitro digestion profile was significantly correlated.     

Effects of jet-cooking conditions upon intrinsic viscosity and flow properties of starches

This work examined the sensitivity of intrinsic viscosity values of jet-cooked waxy maize starch to initial pH conditions and the effects of jet-cooker steam pressure parameters upon the intrinsic viscosity and flow viscosity values of four jet-cooked starches. Flow viscosities of the 10 wt % cooked starches and intrinsic viscosities in 90% DMSO-H₂O were the lowest when mixing and turbulence during steam jet-cooking was increased (i.e., by adjusting steam line pressure vs. pressure within the cooking chamber to allow greater amounts of steam to flow through the apparatus). The percent decreases of the intrinsic viscosity caused by the most severe cooking conditions compared to gentle cooking conditions were 52, 45, 32, and 12, respectively, for waxy maize, waxy rice, normal maize, and 70% high amylose maize starches. Initial pH values, from 3 to 10.5, of waxy maize starch had minor effects upon the intrinsic viscosity of the jet-cooked material. © 1996 John Wiley & Sons, Inc.

1 This is a U.S. Government work and, as such, is in the public domain in the United States of America.

     

智能响应型Pickering乳液的制备及在物质分离中的应用进展

Pickering乳液是指由微纳米固体粒子代替传统表面活性剂作为乳化剂而稳定的乳液,具有较强的稳定性和超高油/水界面,能够为多相界面反应和物质传输提供高效稳定的场所。Pickering乳液的乳滴结构和性质与固体颗粒的尺寸形貌及表面性质密不可分,通过调控固体颗粒本身或表面的性质可以赋予Pickering乳液特定的响应性功能,拓宽其应用领域。本文对近年来不同响应型（磁性、CO₂、pH、光、温度等响应型）的Pickering乳液的主要研究成果进行了综述,重点介绍了Pickering乳液的稳定性原理、响应型Pickering乳液的制备方法和结构调控策略,以及近年来Pickering乳液在物质分离提取中的应用研究进展,最后对智能响应型Pickering乳液应用研究的发展趋势进行了展望。     

机械活化对玉米淀粉结晶结构与化学反应活性的影响

采用搅拌球磨机对玉米淀粉进行机械活化，用X射线衍射仪、差示扫描量热仪、扫描电子显微镜及粒度分析仪等考察了机械活化对玉米淀粉结晶结构、热特性、颗粒形貌及粒度变化的影响。并将不同活化时间的玉米淀粉在相同条件下与乙酸酐进行酯化反应及与丙烯酰胺进行接枝共聚反应，通过研究机械活化对酯化反应取代度、接枝共聚反应接枝率与接枝效率的影响规律来探讨机械活化对玉米淀粉化学反应活性的影响。结果表明，机械活化预处理能显著提高玉米淀粉酯化反应的取代度及接枝共聚反应的接枝率与接枝效率，说明机械活化能有效地提高玉米淀粉的化学反应活性。其原因是玉米淀粉在机械活化过程中其结晶结构与颗粒形貌均受到破坏，结晶度降低，最终由多晶态转变成非晶态。并随活化时间的延长，糊化温度及糊黏度下降，流动性增强，从而使反应试剂的扩散阻力下降，易于扩散到淀粉分子中参与反应。     

Synthesis and Characterization of Maize Starch Acetates and its Biodegradable Film

Starch acetates (SA) were synthesized by maize starch reacting with acetic acid/acetic anhydride, using sulfuric acid as catalyst. The biodegradable films were produced by thermal gelatinization of starch suspensions blending raw starch or SA with different degree of esterification (DS) and polyvinyl alcohol (PVA). Fourier transform infrared spectrogram (FT-IR) data showed acetate was introduced into the molecule chain of starch. Different structure of aggregation supported between the modified starch and the raw starch was determined by the scanning electron microscopy (SEM). Differential scanning calorimetry indicated SA glass transition temperature reduced with increasing of its DS. X-ray diffraction pattern of SA revealed the crystallinity of chain starch was destroyed, forming many completely even amorphous areas. SEM studies showed that amorphous was raised with DS of starch acetates. The mechanical and hydrophobic properties of the films were better than those of raw starch/PVA. In 50 days outdoor soil burial biodegradable experiment in summer, the weight loss of the films was almost 50%.     

Janus graphene oxide nanosheets prepared via Pickering emulsion template

Janus graphene oxide (GO) nanosheets functionalized by amino-containing chemicals were prepared via Pickering emulsion template. A wax-in-water Pickering emulsion was used to mask one side of GO nanosheets in order to achieve asymmetric chemical functionalization. Janus particles were obtained by removing the oil phase. The successful reaction of epoxy groups on the surface of GO with amino-containing chemicals was confirmed by Fourier transform infrared spectroscopy (FT-IR) and thermal gravimetric analysis (TGA). The asymmetric surface structure of Janus GO nanosheets was detected by atomic force microscope (AFM) and X-ray diffraction (XRD). The efficient stabilization of an oil-in-water Pickering emulsion by Janus GO was proved. Polymer microspheres fabricated by using Janus GO as Pickering stabilizer had a more hydrophilic surface compared with those stabilized by symmetrically modified GO.