化学改性淀粉的研究进展

综述了化学改性淀粉的研制及应用现状,评价了各种改性淀粉的应用性能并预测了其今后的发展趋势.     

Effect of Microwave Irradiation on Acid Hydrolysis of Faba Bean Starch: Physicochemical Changes of the Starch Granules

Starch is the most abundant carbohydrate in legumes (22–45 g/100 g), with distinctive properties such as high amylose and resistant starch content, longer branch chains of amylopectin, and a C-type pattern arrangement in the granules. The present study concentrated on the investigation of hydrolyzed faba bean starch using acid, assisted by microwave energy, to obtain a possible food-grade coating material. For evaluation, the physicochemical, morphological, pasting, and structural properties were analyzed. Hydrolyzed starches developed by microwave energy in an acid medium had low viscosity, high solubility indexes, diverse amylose contents, resistant starch, and desirable thermal and structural properties to be used as a coating material. The severe conditions (moisture, 40%; pure hydrochloric acid, 4 mL/100 mL; time, 60 s; and power level, 6) of microwave-treated starches resulted in low viscosity values, high amylose content and high solubility, as well as high absorption indexes, and reducing sugars. These hydrolyzed starches have the potential to produce matrices with thermo-protectants to formulate prebiotic/probiotic (symbiotic) combinations and amylose-based inclusion complexes for functional compound delivery. This emergent technology, a dry hydrolysis route, uses much less energy consumption in a shorter reaction time and without effluents to the environment compared to conventional hydrolysis.     

微波辅助酶促月桂酸淀粉酯的合成

以天然玉米淀粉和月桂酸为原料,脂肪酶Novozym 435为催化剂,研究了微波辐照下月桂酸淀粉酯的酶促合成。通过对淀粉进行预处理活化来提高淀粉的酯化反应活性,并主要考察了微波功率、月桂酸用量、脂肪酶Novozym 435用量及反应时间等参数对酶促月桂酸淀粉酯合成的影响。采用气相色谱法进行取代度的测定,并以取代度为考察指标,确定了最佳的反应条件。结果表明,淀粉的最佳预处理方法为NaOH/尿素混合溶液法,经该法处理后淀粉的酯化反应活性大大提高;微波辐照技术的应用大大缩短了反应时间,并提高了月桂酸淀粉酯的取代度。适宜的工艺条件为：微波功率为240W,月桂酸用量为30%,酶加入量为7%,反应时间26min。在上述反应条件下可以制得取代度为 0.0311的月桂酸玉米淀粉酯。     

具有低表面能的改性淀粉纳米晶的制备

通过端异氰酸酯基与淀粉纳米晶表面的部分羟基反应,引入聚二甲基硅氧烷分子,制备表面能低、分散稳定的改性淀粉纳米晶。通过红外光谱(FT-IR)、核磁共振氢谱(1 H-NMR)、光电子能谱(XPS)、X射线衍射仪(XRD)、扫描电镜(SEM)等对其结构和形貌进行表征。结果表明,低表面能有机硅分子和二苯甲基二异氰酸酯反应到淀粉纳米晶上,其纳米颗粒粒径为50~100nm,分散均匀。此外,浸润性实验表明,改性淀粉纳米晶在水、二氯甲烷、乙酸乙酯、丙酮中分散稳定。     

烟丝含水率对其燃烧性的影响研究

采用同步热分析技术考察了不同湿度下平衡后的烟丝燃烧性。结果表明:1烟丝含水率随着平衡湿度的增加而增加,并存在一定的线性相关;2通过比较每一阶段的失重率可知,烟丝不同含水率对其燃烧和热解反应的各个阶段有一定影响,失重率随着平衡湿度变化的转折点在平衡湿度50%~60%之间;3烟丝的燃烧特性指数Sn随着平衡湿度的增加而减小,平衡湿度与烟丝含水率、平衡湿度与平均燃烧速度间呈显著正相关,着火温度与燃烧特性指数间呈显著负相关,而平衡湿度与燃烧特性指数Sn无显著的相关性。     

Properties of High-Swelling Native Starch Treated by Heat–Moisture Treatment with Different Holding Times and Iterations

Tapioca and potato starches were used to investigate the effect of heat–moisture treatment (HMT; 95–96 °C, 0–60 min, 1–6 iterations) on gelatinization properties, swelling power (SP), solubility and pasting properties. Tapioca starch had similar content and degree of polymerization of amylose, but a higher amylopectin short/long chain ratio, to potato starch. After HMT, the gelatinization temperature range was narrowed for tapioca starch, but was widened for potato starch. Decreases in SP and solubility were less for tapioca than potato starches, coinciding with a progressive shift to the moderate-swelling pasting profile for tapioca but a drastic change to the restricted-swelling profile for potato. Moreover, decreasing extents of SP and maximum viscosity for HMT tapioca starch were, respectively, in the range of 47–63% and 0–36%, and those of HMT potato starch were 89–92% and 63–94%. These findings indicate that the granule expansion and viscosity change of starch during gelatinization can be tailored stepwise by altering the HMT holding time and iteration.     

Enhancing Resistant Starch Content of High Amylose Rice Starch through Heat–Moisture Treatment for Industrial Application

The objective of the present study is to enhance the resistant starch (RS) content of high amylose rice starch with heat–moisture treatment (HMT) for industrial application. The optimized HMT condition for achieving the highest RS content established using response surface methodology (RSM) was a temperature of 100 °C, moisture content of 24.2%, and a time of 11.5 h. Upon HMT, the RS content increased from 32.1% for native starch to 46.4% in HMT starch with optimized condition. HMT of the starches reduced the solubility and swelling power. The surface of HMT starch granules was more irregular than native starch. The X-ray diffraction (XRD) peak intensity at 2θ = 5° was greatly reduced by HMT, and the peaks at 22.7° and 24.2° were merged. HMT increased the gelatinization temperature and reduced the gelatinization enthalpy. HMT provides a method for the production of high-yield RS2 with high amylose rice starch in industrial application.     

接枝共聚改性氧化淀粉及电流变性研究

通过自由基接枝共聚的方法，合成了改性的氧化淀粉-BA—MAA—Gd共聚物，采用红外光谱、扫描电镜、同步热分析、x射线粉末衍射等方法对产物进行了结构表征。用接枝物制备了电流变液，测定了在不同接枝物含量和电场强度下体系的电流变效应。实验结果表明：该电流变液体系的剪切应力随着电场强度的增大而增大；而在相同电场强度下，剪切应力则随电流变液中接枝物含量的增加而增大。     

Impact of Cassava Starch Varieties on the Physiochemical Change during Enzymatic Hydrolysis

The enzymatic modification of starch extends its industrial use to flavor delivery and probiotic encapsulants, among other uses. However, it is not known how starch from different cassava varieties responds to enzymatic hydrolysis. Starches from two Ecuadorian cassava varieties (INIAP 650, an edible starch, and INIAP 651, an industrial starch) were partially modified at three enzymatic hydrolysis degrees (0%, 30%, and 50%), and their physicochemical properties were assessed. The structural analysis revealed that both varieties showed progressive structural damage as hydrolysis increases, probably due to exo-hydrolysis. However, deeper pores were observed in INIAP 651 with the SEM analysis. The crystallinity percentage obtained by XRD analyses remained constant in INIAP 651 and decreased (by 26%) in INIAP 650 (p < 0.05). In addition, the amylose–lipid complex index in INIAP 650 remained constant, while INIAP 651 increased (p < 0.05) at 30% hydrolysis (by 93%). In both varieties, hydrolysis increased (p < 0.05) the water holding capacity (WHC) (by 10–14%) and the water binding capacity (WBC) (by 16%), but 50% hydrolysis of INIAP 650 was needed to significantly affect these properties. No differences were observed in the varieties’ thermal properties. Regarding the rheological properties, the variety did not influence the changes in the storage module (G′) and the loss modulus (G″) with the hydrolysis (p > 0.05). However, the phase angle decreased significantly (p < 0.05) with the hydrolysis, being higher in the INIAP 650 variety than in the INIAP 651 variety. In general, the results indicate that the variety affects the response of the starch granule to enzymatic hydrolysis (noticeable in the principal component analysis, PCA) and opens up the possibility to modulate starch properties.     

微波对酶催化反应的影响及其微波效应的研究进展

综述了近年来微波对酶催化反应的影响,包括对酶催化反应速度与转化率或产率的影响,对酶促反应选择性与专一性的影响,对酶结构和活性的影响.总结了研究微波效应的几种技术方法及其在酶催化反应中的应用情况.     

微波对碱式碳酸镁结晶过程的影响

在微波外场作用下,利用氯化镁和碳酸钠溶液反应结晶法直接合成碱式碳酸镁晶体。通过对比微波、水浴两种加热方式下镁离子变化曲线和产物的差异,XRD、FTIR,SEM等对相转移过程的物相分析表征,探索微波对反应的强化影响。结果表明,反应结晶直接合成碱式碳酸镁过程分为絮状物→出现晶体→完全转变为球状碱式碳酸镁3个阶段。微波对反应3个阶段中都有强化作用,促进絮状物的形成,加快相转变,提高反应转化率,微波加热条件下在粒径分布与组装方式与水浴加热方式均有不同,微波作用下较小颗粒是由纳米片层平行组装而成,而较大颗粒可能是无定形物在球状小颗粒表面继续转变,形成交错的表层纹理的大颗粒碱式碳酸镁。     

Effect of Long-Term Potato Starch Retention with Citric Acid on Its Properties

The present study aimed to determine changes in the properties of starch triggered by its long-lasting (1, 2, 4, 7, 10, or 14 days) retention with citric acid (5 g/100 g) at a temperature of 40 °C. The starch citrates obtained under laboratory conditions had a low degree of substitution, as confirmed via NMR and HPSEC analyses. The prolonging time of starch retention with citric acid at 40 °C contributed to its increased esterification degree (0.05–0.11 g/100 g), swelling power (30–38 g/g), and solubility in water (19–35%) as well as to decreased viscosity of the starch pastes. Starch heating with citric acid under the applied laboratory conditions did not affect the course of DSC thermal characteristics of starch pasting. The low-substituted starch citrates exhibited approximately 15% resistance to amylolysis.     

微波辐射对淀粉结构及性质的影响

简单地介绍了微波对淀粉的辐射作用,并综述了微波辐射对淀粉形态结构和结晶结构以及淀粉凝胶化性质、热性质等影响的国内外研究进展,如微波辐射可改变淀粉颗粒形状、结晶结构及其结晶度.微波辐射时间及辐射能等技术参数能够改变淀粉的凝胶化性质,而淀粉的含水量也是重要的影响因素.淀粉的溶解性、润胀性和吸水性都会因微波辐射而较原淀粉下降.     

Effect of different starch contents on physical,morphological, mechanical,barrier, and biodegradation properties of tapioca starch and poly(butylene adipate-co-terephthalate) blend film

Study on degradation behaviors of biodegradable poly(butylene adipate-co-terephthalate) (PBAT) blended with different compositions of thermoplastic starch (TPS) under soil burial and natural weathering environments is vital in order to predict the product service-life and planning for in situ biodegradation after product disposal. In this article, different compositions of TPS (0%, 20%, 40%, 50%, and 60%) were compounded with PBAT using single screw extruder. The samples were characterized for their tensile properties, fractured surface morphology, water barrier and surface hydrophorbicity properties in order to investigate the effect of starch fractions in PBAT blends. The degradation behavior under natural weathering and soil burial conditions was also determined during the 9 months duration by observing the change of physical appearance, weight loss, surface morphology, chemical structural, and tensile properties. The findings showed that the addition of TPS (20%, 40%, 50%, and 60%) had led to a reduction in tensile strength (41.47%, 60.53%, 63.43%, and 68.53%), and reduction in elongation at break (42.92%, 92.1%, 92.23%, and 93.22%, respectively) and water barrier properties. The findings also showed that there were distinct degradation behavior under both conditions. Upon exposure to natural weathering, photodegradation and Norrish type I & II occurred whereas under the soil burial condition, hydrolytic, and enzymatic degradation take places. Sample with the highest starch contents underwent the highest weight loss and reduction in tensile properties under both environments. The findings in this study are useful in order to investigate the feasibility of PBAT/Tapioca starch blends for biodegradable plastic film for various industrial applications especially in packaging and agricultural mulch.     

Effect of High Humidity Exposure to Wheat Starch Based High Conducting Flexible Polymer-in-Salt-Electrolyte

Polymer-in-salt-electrolytes (PISEs) are an important class of electrolytes as they carry the promise of faster and single ion transport. Unfortunately, due to unavailability of a suitable polymer host PISE has still not reached to commercial level. In the present work, using a novel synthesis protocol developed by the group, glutaraldehyde crosslinked wheat starch has been successfully modified with sodium iodide (NaI) to synthesize a flexible PISE membrane with desired electrochemical properties. Present paper reports the effect of crosslinker and exposure to high humidity ambience on electrochemical and morphological properties. It has been established that on exposure to higher humidity atmosphere starch-based PISEs stabilize at lower resistance value, but with higher ion relaxation time, which indicates that effect of high humidity treatment is more on salt dissociation instead of assisting the ion transport. The studied materials have conductivity ≈0.01 S cm⁻¹ range with ESW >2.5 V, ensuring its usability in electrochemical devices. The developed synthesis protocol does not require any complicated synthesis route and/or sophisticated instrument hence the overall process is economical also, adding up to its potentiality for energy device fabrication.     

微波辐射对乙酸乙酯皂化反应的影响

采用电导率法研究了微波辐射对乙酸乙酯皂化反应动力学常数的影响.结果表明,反应物经微波辐射后化学反应的动力学常数增大,且与辐射时间长短呈正相关.分析了微波辐射使动力学常数增大的原因.     

Effect of pH on the Redox and Sorption Properties of Native and Phosphorylated Starches

Starch is a common biopolymer that can be used for removing heavy metal ions from aqueous solutions. A valuable property of starch is its functional diversity, which can be enhanced by chemical modification. Hydroxyl groups enclosed in the starch and formed during hydrolysis act as reducing agents of Cr(VI). The sorption properties of native starch depend mainly on the presence of carboxyl groups formed during redox processes and basic centers created during acid hydrolysis, while the superiority of phosphorylated starch is related to the presence of phosphate groups binding Cr(III) ions. The effectiveness of starch depends on a series of equilibria established in its aqueous suspension and chromate ions solution, where the pH is the driving force for these processes. In this article, a systematic discussion of pH changes being the consequence of chemical reactions unraveling the extraordinary functionalities of starch was given. It also explained the influence of establishing equilibria and chemical modifications of starch on the efficiency of chromium ion removal. This allowed for the development of a comprehensive mechanism for the interaction of Cr(VI) and Cr(III) ions with native and phosphorylated starch.     

Effects of Different Extraction Methods on the Gelatinization and Retrogradation Properties of Highland Barley Starch

The purpose of this study was to compare the gelatinization and retrogradation properties of highland barley starch (HBS) using different extraction methods. We obtained HBS by three methods, including alkali extraction (A-HBS), ultrasound extraction (U-HBS) and enzyme extraction (E-HBS). An investigation was carried out using a rapid viscosity analyzer (RVA), texture profile analysis (TPA), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and Fourier-transform infrared spectrometry (FTIR). It is shown that the different extraction methods did not change the crystalline type of HBS. E-HBS had the lowest damaged starch content and highest relative crystallinity value (p < 0.05). Meanwhile, A-HBS had the highest peak viscosity, indicating the best water absorption (p < 0.05). Moreover, E-HBS had not only higher G′ and G″ values, but also the highest gel hardness value, reflecting its strong gel structure (p < 0.05). These results confirmed that E-HBS provided better pasting stability and rheological properties, while U-HBS provides benefits of reducing starch retrogradation.     

Assessment of Microwave Effect on Polymerization Conducted under ARGET ATRP Conditions

A comprehensive kinetic model based on the method of moments is developed for understanding the kinetics of activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) under microwave irradiation. Both the experimental data and the simulation results show that the polymerization under microwave irradiation is much faster than the thermal polymerization. Simulation results indicate that the acceleration of polymerization can be attributed to the increase of propagation rate coefficient and the radical generation by microwave irradiation. Kinetic behaviors, such as the effect of catalyst concentration and initial initiator, are investigated in detail. Results show that the catalyst concentration has negligible influence on polymerization rate while the initiator concentration can affect both the molecular weight and the reaction rate. In conclusion, this work thoroughly investigates the kinetic mechanism of ARGET ATRP under microwave irradiation, providing both theoretic and experimental supports to improve the product property of polymer materials.