Biosysthesis of corn starch palmitate by lipase novozym 435

Esterification of starch was carried out to expand the usefulness of starch for a myriad of industrial applications. Lipase B from Candida antarctica, immobilized on macroporous acrylic resin (Novozym 435), was used for starch esterification in two reaction systems: micro-solvent system and solvent-free system. The esterification of corn starch with palmitic acid in the solvent-free system and micro-solvent system gave a degree of substitution (DS) of 1.04 and 0.0072 respectively. Esterification of corn starch with palmitic acid was confirmed by UV spectroscopy and IR spectroscopy. The results of emulsifying property analysis showed that the starch palmitate with higher DS contributes to the higher emulsifying property (67.6%) and emulsion stability (79.6%) than the native starch (5.3% and 3.9%). Modified starch obtained by esterification that possesses emulsifying properties and has long chain fatty acids, like palmitic acid, has been widely used in the food, pharmaceutical and biomedical applications industries.     

酶促酯化制备松香酸淀粉酯的性质及结构表征

以松香和木薯淀粉为原料,二甲基亚砜（DMSO）为溶剂,采用酶催化酯化法在温和条件下制备了取代度0.031～0.092的松香酸淀粉酯,并对其部分理化性质进行了研究。结果表明：松香酸淀粉酯的性能与其取代度密切相关。随着取代度的增大,酯化淀粉产物的可溶指数和溶胀度降低,相对黏度和特性黏度增强,分子链也随取代度的增大而增加。通过对淀粉-碘络合物的紫外光谱分析,发现随着取代度的增大,酯化产物的最大紫外吸收波长向长波长方向移动,且蓝值减小。红外光谱（FT-IR）、核磁氢谱（¹H NMR）、差示热扫描（DSC）、热重差（TGA）和扫描电镜（SEM）对不同取代度的松香酸淀粉酯表征分析的结果表明：酯化产物在1727 cm^-1处产生C O的特性吸收峰,糊化温度及热稳定性相对预处理淀粉有所降低,淀粉颗粒的结晶度下降。     

高直链淀粉醋酸酯的合成与表征

以高直链玉米淀粉为原料 ,甲磺酸为催化剂 ,制备一系列不同取代度的淀粉醋酸酯 ,研究了不同反应时间、温度、催化剂用量等对取代度的影响。结果表明 :反应时间越长 ,取代度越大 ,特性粘度变小 ;随着反应温度的升高 ,取代度增大 ,但特性粘度却明显降低 ;随着酸与酸酐用量的提高 ,取代度逐渐提高 ,特性粘度下降 ;增加 MSA用量 ,可大大提高取代度。应用 FTIR、XRD、DSC等近代测试手段 ,对淀粉醋酸酯样品进行了结构表征。     

Carboxymethylation of γ‐irradiated starch

Low viscosity carboxymethyl corn starch was prepared by the reaction of γ‐irradiated starch with monochloroacetic acid in the presence of alkali. It was found that irradiation dose influences the product viscosity remarkably. The viscosity decreases as the irradiation dose level increases; however, the viscosity increases with the increasing dose rate and the degree of substitution (DS). γ‐Irradiation can activate the starch to react with monochloroacetic acid, and the more of the irradiation dose, the higher of the DS and the reaction efficiency. The product has the character of low viscosity at high concentration, and the more of the irradiation dose, the more similar of the rheological behavior to a Newtonian liquid. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2210–2215, 2006     

机械活化对木薯淀粉醋酸酯化反应的强化作用

采用搅拌球磨机对木薯淀粉进行机械活化,以不同活化时间的木薯淀粉为原料,以醋酸酐为酯化试剂、甲磺酸为催化剂制备淀粉醋酸酯,并以取代度为评价指标,分别研究了机械活化时间、反应时间、反应温度、催化剂用量及醋酸酐用量对木薯淀粉醋酸酯化反应的影响. 结果表明,机械活化对木薯淀粉酯化反应有显著的强化作用,活化时间越长,取代度越高. 主要原因是机械活化使木薯淀粉紧密的颗粒表面和结晶结构受到破坏,降低了结晶度,酯化试剂更容易渗透到颗粒内部使淀粉醋酸酯化. 其他因素对淀粉酯化反应的影响规律受活化时间的制约,活化时间越长,酯化反应对反应温度、催化剂及醋酸酐浓度的依赖性越低. 并利用红外光谱对木薯淀粉、活化淀粉及高取代度淀粉醋酸酯的结构进行了表征.     

Synthesis of starch esters in ionic liquids

Chemical modification of corn starches with succinic anhydride or acetic anhydride was carried out using 1‐butyl‐3‐methylimidazolium chloride (BMIMCl) as a reaction medium. The reaction progress was followed in terms of the degree of substitution (DS) for the starch derivatives. The results showed that the homogeneous esterification of starch at 5 : 1 molar ratio of anhydride/anhydroglucose units at 100°C led to formation of acetates with DS ranging from 0.37 to 2.35 and succinates with DS ranging from 0.03 to 0.93. Moreover, the reaction media applied could be easily recycled and reused. Further, the formation of starch esters was confirmed by the presence of the carbonyl signal in the FTIR and NMR spectra. It was shown that the starch granules were mostly converted from their crystalline structure into amorphous state in the ionic liquid system under the given reaction conditions. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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 of starch benzoate in aqueous media

Summary The results of investigating starch benzoate (SB) synthesis in aqueous media are presented in this study. Starch esterification with benzoyl chloride was performed in two steps, the first step being the alkalization of starch and the second step esterification. The influence of the concentration of reactants, reaction medium composition, temperature and time of synthesis on the degree of substitution (DS), degree of swelling in water and thermal stability of the synthesized starch benzoate was investigated. The optimal conditions for the synthesis of starch benzoate with degree of substitution from 0.23 to 1.76 were determined. It was shown that starch benzoate with a DS of 1.76 practically did not swell in water. However, starch benzoate is less thermally stable than native starch probably due to a change in the supermolecular order induced by the esterification reaction. Received: 18 March 2002/Revised version: 18 October 2002/ Accepted: 28 October 2002 Correspondence to Katarina Jeremić     

Investigations on esterification reactions of starches in 1‐N‐butyl‐3‐methylimidazolium chloride and resulting substituent distribution

The ionic liquid (IL) 1‐N‐butyl‐3‐methylimidazolium chloride ([C₄mim]⁺Cl^?) was used as solvent for different esterification reactions of the biopolymer starch. Therefore, maize starches with varying content of amylose were used. Different carboxylic acid anhydrides were applied to esterify starch with a degree of substitution (DS) in the range of 0.7–3.0. For example, starch acetates with the mentioned DS are accessible within 30 min at a 105°C‐reaction temperature. The DS distribution of starch acetates synthesized in IL was compared with the common starch acetate synthesis of Mark and Mehltretter. Also, a consideration of starch acetates and cellulose acetates synthesized in [C₄mim]⁺Cl^? is given. The starch esters were characterized by means of Raman spectroscopy for qualitative‐ and nuclear magnetic resonance spectroscopy for quantitative determination of the functionalization pattern. Moreover, the molecular mass distribution was determined after saponification by means of GPC‐MALLS. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

共反应剂法合成金刚烷甲酸纤维素酯

In order to develop a novel bioactive material utilizing cellulose resource, adamantane carboxylic acid esters of cellulose were synthesized through in-situ activation of the adamantane carboxylic acid using N,N-dimethylacetamide/LiCl as solvent, p-toluenesulfonyl chloride as co-reagent.The structure and properties of adamantane carboxylic acid esters of cellulose were characterized by means of IR, ¹H NMR, TG,etc.The esterification conditions were investigated in detail.The results showed that the degree of substitution was influenced by reaction temperature, reaction time and mole ratios of repeat units of cellulose/adamantane carboxylic acid/p-toluenesulfonyl chloride.Under the optimized reaction conditions, the highest degree of substitution (DS) was 1.9.TG analysis revealed that the thermal stability of cellulose esters was improved with the increase of DS due to the incorporation of adamantane carboxylic acid into chains of cellulose.The products are soluble in various organic solvents, depending on the DS.     

Effect of amphiphilic phosphate/octenylsuccinate starch on enhancing adhesion to hydrophobic polyester fibers in sizing

Amphiphilic starch at different degree of substitution (DS) was prepared by phosphorylation and octenylsuccinylation of acid-thinned starch with sodium tripolyphosphate and 2-octenylsuccinic anhydride, respectively for improving the adhesion of starch to polyester fibers. Various assessment of starch such as ¹H NMR and FTIR analysis, apparent viscosity, starch clarity, adhesion to polyester fiber, desizing efficiency and biodegradability were conducted. The ¹H NMR and FTIR spectroscopy revealed that octenylsuccinate and phosphate substituents have been attached to the molecular chain of starch. Also, the apparent viscosity, paste clarity, desizing efficiency and biodegradability of the amphiphilic starch increased as the DS of phosphate increased. It was observed that the amphiphilic starch was an effective method for stronger adhesion unto polyester fibers but reduced at the highest DS of phosphate due to excessive hydrophilicity. As compared to acid-thinned starch, the stronger adhesion of the amphiphilic starch was attributed to the steric hindrance caused by the two substituents on starch and the good dispersibility impacted by the phosphate substituents on starch. Conclusively, the strongest adhesion on polyester fibers, good paste clarity, good desizing efficiency and enhanced biodegradability of starch were attained at phosphate and octenylsuccinate DS ratio of 0.031/0.014.     

一次羧甲基化制备高取代度(DS=2.20)羧甲基玉米淀粉

通过一次羧甲基化制备了DS=2.20的高取代度羧甲基玉米淀粉(CMCS)。研究了氢氧化钠用量、反应介质、反应时间和反应温度对反应效率(RE)和取代度(DS)的影响。当n(NaOH)/n(AGU)=4时,最佳反应条件为n(NaOH)/n(ClCH2COOH)=2.5、异丙醇中φ(水)=2.4%、反应温度50℃、反应时间2h,在最佳反应条件下制得CMCS的DS=2.20,RE=55%。另外,用红外光谱证明了CMCS中存在羧甲基结构。     

Controlled heterogeneous modification of cellulose fibers with fatty acids: Effect of reaction conditions on the extent of esterification and fiber properties

The controlled heterogeneous partial modification of cellulose fibers with fatty acids, partially preserving the fiber structure, was investigated. The effect of reaction conditions, such as reaction time, fatty acid chain length, and solvent types (swelling and non swelling), on the extent of esterification and fiber properties was evaluated by elemental analysis, IR‐ATR, X‐ray diffraction, ¹³C CPMAS NMR, contact angle measurement, thermogravimetry, and scanning electron microscopy. The degree of substitution (DS) increased with reaction time and with the swelling effect of the reaction medium and decreased with the fatty acids chain length. Higher the DS, higher is the decrystallization of cellulose as a result of the heterogeneous esterification reaction. The esterification with fatty acids enhanced the hydrophobic character of the fibers, but decreased their thermal stability. These properties are not strongly affected by the DS in the range investigated, viz. up to 1.4. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1093–1102, 2006     

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%.     

Optimization of preparation conditions of carboxymethyl potato starch through orthogonal experimental design

To optimize the preparation conditions of carboxymethyl potato starch (CMPS), the effects of relevant factors on viscosity (η) of 2% CMPS aqueous solution and degree of substitution (DS) were investigated. These condition parameters included etherification temperature, alkalization and etherification time, water content in the mixed solvent, ratio of liquid volume to starch mass, molar ratio of sodium hydroxide to monochloroacetic acid, and molar ratio of monochloroacetic acid to anhydroglucose unit. After individual parameter influencing η and DS was researched one by one, an orthogonal experiment of L₁₈ (2 × 3⁷) was designed to identify the main factors affecting them. In light of range analysis, the comparative importance of factors impacting η and DS was obtained, separately. Results of variance analysis showed that the most effective factor to control DS was etherification temperature, whereas the influences of all factors on η were not significant. Meanwhile, η and DS of the optimized final product were found to be 12,000 mPa.s and 0.68, respectively. In addition, the structure of CMPS was characterized by Fourier transform infrared (FTIR) spectrophotometer. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

超声波强化制备高取代度大米淀粉乙酸酯

高取代度乙酸酯(DS>2)由于其热塑性及疏水性, 在高分子领域应用广泛。以大米淀粉为原料, 对甲苯磺酸为催化剂, 在冰乙酸/乙酸酐体系中, 采用了超声强化方法制备高取代度乙酸酯淀粉, 并用FTIR、XRD 和SEM对产物进行表征。考察了超声作用时间、超声温度、超声功率对大米淀粉乙酸酯取代度(DS)的影响, 并用响应面法对超声条件进行了优化, 得到的最佳工艺如下:超声时间为15.67min, 超声温度为31.33℃, 超声功率为85.60W, 在此条件下, 得到的乙酸酯淀粉的取代度为2.77。由FTIR图谱可知, 乙酸酯淀粉在1750cm^-1、1433cm^-1、1375cm^-1及1239cm^-1处出现了乙酰基的特征峰, 证明成功地制得了高取代度乙酸酯淀粉。XRD和SEM结果表明, 乙酰化后淀粉的结构完全被破坏。研究结果为高取代度淀粉乙酸酯的工业生产提供了依据。     

Ultrasound effects on the acetylation of dioscorea starch isolated from Dioscorea zingiberensis C.H. Wright

The objective of current work is to investigate the intensification of starch towards acetylation by acetic anhydride after ultrasound treatment. Native dioscorea starch (NDS) slurry was ultrasonically treated to produce ultrasound-treated dioscorea starch (UTDS). The effects of ultrasound-treated conditions of NDS on degree of substitution (DS) of ultrasound-treated dioscorea starch acetate (UTDSA) were examined. The influences of different acetylation conditions such as reaction time, reaction temperature and the molar ratios of H₂SO₄ to starch on the DS of starch acetate (SA) were also investigated by comparing the DS of UTDSA with NDSA's. The results demonstrate that a higher DS value is always observed for the acetylation of UTDS sample under the same reaction conditions. Moreover, using UTDS or NDS as material, the SAs with same DS value (0.55 and 1.75) were synthesized, and their chemical structure, crystalline structure, thermal stability, and morphological properties were characterized by the Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) techniques.     

经皮给药用酯化淀粉基压敏胶的制备与性能研究

以淀粉为主要原料、脂肪酸为淀粉的酯化改性剂、三氯氧磷为化学交联剂、水和甘油为增塑剂,制备了一系列经皮给药用亲水性酯化淀粉基PSA(压敏胶)。采用红外光谱(FT-IR)法对酯化淀粉的结构进行了表征,考察了脂肪酸中碳链长度、交联剂含量和取代度(DS)等对PSA性能的影响,并研究了该PSA中5-氟尿嘧啶(5-FU)和布洛芬(IBU)的经皮渗透行为。结果表明:当m(淀粉粉末)∶m(水)∶m(甘油)=1.0∶0.5∶0.5、w(三氯氧磷)=1.0%和DS=0.086 8时,辛酯淀粉基PSA具有适宜的力学性能,符合经皮给药系统用PSA的使用要求,而且其对5-FU、IBU的经皮渗透性能具有较好的调控作用。     

高取代度阳离子淀粉的合成与表征

以玉米淀粉为原料,N-(2,3-环氧丙基)三甲基氯化铵(GTA)为阳离子醚化剂,在碱催化条件下,制备了高取代度阳离子淀粉,研究了反应条件对产品取代度和结构的影响。结果表明,在n(NaOH)/n(淀粉葡萄糖基AGU)=0.2025,n(GTA)/n(AGU)=4.0,反应温度60℃的条件下反应6h,取代度可达1.0959。用FTIR和13CNMR表征了高取代度阳离子淀粉的结构,X-ray衍射结果表明,阳离子化反应破坏了原淀粉的结晶结构,生成了具有非晶态结构的阳离子淀粉。     

高取代度羧甲基淀粉的制备

用玉米淀粉、氯乙酸和氢氧化钠为原料，在乙醇溶剂中反应制备了取代度为０．６的羧甲基淀粉。采用正交设计试验考察了物料配比、反应温度、反应时间对产物取代度的影响，确定了最佳反应条件。