辛烯基琥珀酸淀粉酯的脂肪酶耦合合成及其性质研究
摘要
本文主要研究脂肪酶耦合酯化反应,以玉米淀粉为原料制备辛烯基琥珀酸淀粉酯的工艺,并研究了所得淀粉酯的基本性质。
首先研究了脂肪酶在磷酸缓冲液、有机溶剂体系、淀粉糊状态三种不同体系中的催化活性,同时研究了微波辐射对酯化反应的影响。试验证明在一定温度下淀粉吸水膨胀后,即在淀粉成糊状态下,进行酯化反应,此时脂肪酶活性较高,反应效率高。
脂肪酶在玉米淀粉糊状态下,催化其与辛烯基琥珀酸酐反应,可制取具有两亲性质的辛烯基琥珀酸淀粉酯。试验研究了淀粉前处理时间,前处理温度,脂肪酶加入量,反应温度,辛烯基琥珀酸酐加入量,反应时间对产物取代度、反应效率的影响。通过正交试验得到酯化最优组合:淀粉前处理温度为65℃,前处理时间15分钟,反应温度40℃,脂肪酶和辛烯基琥珀酸酐(Octenyl Succinic Anhydride,OSA)的加入量分别是0.5%和6%,反应时间30分钟,可制得取代度为0.024的淀粉酯。
运用现代分析技术对辛烯基琥珀酸淀粉酯的颗粒形态、晶体结构和热力学性质等进行了分析。红外光谱分析表明改性使淀粉分子在波长1713cm~(-1)处有新的吸收峰出现,证明辛烯基琥珀酸基团以酯键的形式与淀粉分子相连。淀粉经过酯化处理后,晶体类型没有发生变化,属于A型,但是淀粉颗粒的表面结构和形状发生很大变化。淀粉改性之后,熔晶的起始温度TO(Onset temperature)、最高温度TP(Peakmaximumtemperature)、回落温度TC(Conelusion temperature)升高,焓变⊿H(Enthalpyoftransition)降低。
论文还研究了辛烯基琥珀酸酸淀粉酯糊的基本性质。玉米淀粉经酯化处理后,常温下凝沉性能升高,溶解度和透明度增加,冻融稳定性有所增强,表观粘度降低。表观粘度测定显示辛烯基琥珀酸淀粉酯具有剪切变稀现象,属于假塑性流体,表观黏度随着温度升高而下降。淀粉酯可用于稳定色拉油-水乳状液。
In this paper the technique of lipase-coupling synthesis of octenly succinic anhydride (OSA) starch using corn starch as raw materials and its properties were studied.
First we investigated the activity of lipase under different conditions: phosphate buffer, organic solvent system and starch paste system, at the same time research about effect of microwave radiation on the impact of esterification reactions was carried out. The results of experiments showed that when starch in paste state after swelling water, the lipase had higher activity and esterification showed higher efficiency.
The pretreatment corn starch could react with alkenyl succinic anhydride under the catalyzing of lipase. The effects of parameters including pretreatment time, pretreatment temperature, reaction time, reaction temperature, quantity of OSA and lipase on DS and react efficiency were studied. The suitable parameters for the preparation were selected as follows: pretreatment time 15 minutes, pretreatment temperature 65℃, reaction temperature 40℃, reaction time 30 minutes, quantity of OSA and lipase 6% and 0.5% respectively. Under the conditions the OSA starch with DS 0.024 was obtained.
The granules morphology, crystal structure and thermodynamic properties of OSA starch were analyzed by the modern analytical techniques. From FT-IR (Fourier transform infrared)results, a new absorption peak appeared at the wavelength of 1713 cm~(-1), which suggested that starch molecules were linked with OSA in the form of ester bond. The X-ray diffraction proved that crystal structure of the modified starch was not changed, belonging to A-pattern as the native corn starch. SEM (Scanning electron microscope) showed the surface of starch granules was seriously destroyed after the reaction. While the DSC (Differential scanning calorimeter) indicated TO (Onset temperature), TP (Peakmaximumtemperature), TC (Conelusion temperature) of modified starch increased, whileΔH (Enthalpyoftransition) decreased.
Moreover, the paste properties of OSA modified starch were investigated. The result showed that under the normal temperature, flocculability, transparency and freeze-thaw stability had been enhanced, while apparent viscosity decreased. The phenomenon of increasing shear force, and decreasing apparent viscosity, showed that it was a kind of Pseudo plastic Fluid. As the temperature increased, the apparent viscosity decreased. The modified starch could be used as emulsifier in the salad oil-water system.
首先研究了脂肪酶在磷酸缓冲液、有机溶剂体系、淀粉糊状态三种不同体系中的催化活性,同时研究了微波辐射对酯化反应的影响。试验证明在一定温度下淀粉吸水膨胀后,即在淀粉成糊状态下,进行酯化反应,此时脂肪酶活性较高,反应效率高。
脂肪酶在玉米淀粉糊状态下,催化其与辛烯基琥珀酸酐反应,可制取具有两亲性质的辛烯基琥珀酸淀粉酯。试验研究了淀粉前处理时间,前处理温度,脂肪酶加入量,反应温度,辛烯基琥珀酸酐加入量,反应时间对产物取代度、反应效率的影响。通过正交试验得到酯化最优组合:淀粉前处理温度为65℃,前处理时间15分钟,反应温度40℃,脂肪酶和辛烯基琥珀酸酐(Octenyl Succinic Anhydride,OSA)的加入量分别是0.5%和6%,反应时间30分钟,可制得取代度为0.024的淀粉酯。
运用现代分析技术对辛烯基琥珀酸淀粉酯的颗粒形态、晶体结构和热力学性质等进行了分析。红外光谱分析表明改性使淀粉分子在波长1713cm~(-1)处有新的吸收峰出现,证明辛烯基琥珀酸基团以酯键的形式与淀粉分子相连。淀粉经过酯化处理后,晶体类型没有发生变化,属于A型,但是淀粉颗粒的表面结构和形状发生很大变化。淀粉改性之后,熔晶的起始温度TO(Onset temperature)、最高温度TP(Peakmaximumtemperature)、回落温度TC(Conelusion temperature)升高,焓变⊿H(Enthalpyoftransition)降低。
论文还研究了辛烯基琥珀酸酸淀粉酯糊的基本性质。玉米淀粉经酯化处理后,常温下凝沉性能升高,溶解度和透明度增加,冻融稳定性有所增强,表观粘度降低。表观粘度测定显示辛烯基琥珀酸淀粉酯具有剪切变稀现象,属于假塑性流体,表观黏度随着温度升高而下降。淀粉酯可用于稳定色拉油-水乳状液。
In this paper the technique of lipase-coupling synthesis of octenly succinic anhydride (OSA) starch using corn starch as raw materials and its properties were studied.
First we investigated the activity of lipase under different conditions: phosphate buffer, organic solvent system and starch paste system, at the same time research about effect of microwave radiation on the impact of esterification reactions was carried out. The results of experiments showed that when starch in paste state after swelling water, the lipase had higher activity and esterification showed higher efficiency.
The pretreatment corn starch could react with alkenyl succinic anhydride under the catalyzing of lipase. The effects of parameters including pretreatment time, pretreatment temperature, reaction time, reaction temperature, quantity of OSA and lipase on DS and react efficiency were studied. The suitable parameters for the preparation were selected as follows: pretreatment time 15 minutes, pretreatment temperature 65℃, reaction temperature 40℃, reaction time 30 minutes, quantity of OSA and lipase 6% and 0.5% respectively. Under the conditions the OSA starch with DS 0.024 was obtained.
The granules morphology, crystal structure and thermodynamic properties of OSA starch were analyzed by the modern analytical techniques. From FT-IR (Fourier transform infrared)results, a new absorption peak appeared at the wavelength of 1713 cm~(-1), which suggested that starch molecules were linked with OSA in the form of ester bond. The X-ray diffraction proved that crystal structure of the modified starch was not changed, belonging to A-pattern as the native corn starch. SEM (Scanning electron microscope) showed the surface of starch granules was seriously destroyed after the reaction. While the DSC (Differential scanning calorimeter) indicated TO (Onset temperature), TP (Peakmaximumtemperature), TC (Conelusion temperature) of modified starch increased, whileΔH (Enthalpyoftransition) decreased.
Moreover, the paste properties of OSA modified starch were investigated. The result showed that under the normal temperature, flocculability, transparency and freeze-thaw stability had been enhanced, while apparent viscosity decreased. The phenomenon of increasing shear force, and decreasing apparent viscosity, showed that it was a kind of Pseudo plastic Fluid. As the temperature increased, the apparent viscosity decreased. The modified starch could be used as emulsifier in the salad oil-water system.
引文
[1]张陈云,任小青.变性淀粉在食品工业中的作用及影响其生产发展的因素.陕西农业科学,2007(1):112-114.
[2]罗勤贵.变性淀粉的生产与应用现状.粮油加工,2006,6(31):50-53.
[3]卢时勇,钱俊青,邹小明等.辛烯基琥珀酸淀粉酯的性能与合成方法.浙江化工,2004,35(2):15-17.
[4]张友松.变性淀粉生产与应用手册.北京:中国轻工业出版社,1999.
[5]Xiaoyan Song,Guoqing He,et al.Preparation and Properties of Octenyl Succinic Anhydride Modified Early Indica Rice Starch.Starch/Staerke,2006,58:109-117.
[6]Atanu Biswas RL,Shogren S,et al.Rapid preparation of starch maleate half-esters.Carbohydrate Polymers,2006,64:484-487.
[7]陈均志,银鹏.微波有机相法制备辛烯基琥珀酸淀粉的研究.粮油食品科技,2004,12(1):16-18.
[8]Method of making lipophilic starch derivatives.Publication number:US4035235.1977-07-12.
[9]辛烯基琥珀酸酯淀粉生产新工艺.中国专利CN1563096,公开(公告)日:2005-01-12.
[10]Imitation cheese products containing modified starch as partial caseinate,replacement and method of preparation.Publication number:US4499116,1985-02-12.
[11]Arvind Viswanathanl.Effect of Degree of Substitution of Octenyl Succinate Starch on the mulsification Activity on Different Oil Phases.Journal of Environmental Polymer Degradation,1999,7:1991-1996.
[12]Rajesh Bhosale,Rekha Singhal.Process optimization for the synthesis of octenyl succinyl derivative of waxy corn and amaranth starches.Carbohydrate Polymers,2006,66:521-527.
[13]卞希良,邬应龙,夏凤清.琥珀酸糯米淀粉酯的制备以及性质的研究.粮油加工与食品机械2006,3:88-91
[14]Rudnik E,Matuschek G,Milanov N & Kettrup A.Thermal properties of starch succinates.Thermochimica Acta,2005,427:163-166.
[15]邓林伟,徐雪芬,袁长贵等.辛烯基琥珀酸淀粉酯(纯胶)的研制和应用研究.食品科技,2002,11:39-41.
[16]马春华,马兴胜.辛烯基琥珀酸淀粉酯在酸奶中的应用.乳业科学与技术,2006,2:68-69.
[17]张燕萍,郑茂强.辛烯基琥珀酸木薯淀粉酯在乳化桔子香精中的应用.无锡轻工大学学报,2004,23(5):74-77.
[18]李香春,甄宗国.脂肪酶特性及其应用.粮食与油脂,2003,3:19-20.
[19]Van Tilbeurg H,Sarda L,Verger R,et al.Structure of the pancreatic lipase procolipase complex.Nature,1992,359:159-162.
[20]魏纪平,熊宁波.固定化脂肪酶催化己酸乙酯的研究.广州食品工业科技,2003,19(1):15-17.
[21]Haas,Michael J.Fuels as solvents for the conduct of enzymatic reactions.US:5697986,1997.
[22]陈志锋,吴虹.固定化脂肪酶催化高酸废油脂酯交换生产生物柴油.催化学报,2006,27(2):146-150.
[23]Sasa Sabeder,Maja Habulin,Zeljko Knez.Lipase-catalyzed synthesis of fatty acid fructose esters.Journal of Molecular Catalysis B:Enzymatic,2006,43:58-62.
[24]Akhila Rajah,V.S.Prasad,T.Emilia Abraham.Enzymatic esterification of starch using recovered coconut oil.International Journal of Biological Macromolecules,2006,39:265-272.
[25]孙君社等.酶与酶工程及其应用.北京:化学工业出版社.
[26]Gbicza L,Kabiri B A,Keoves E,et al.Large-scale enzymatic production of natural flavour esters in organic solvent with continuous water removal.Journal of Biotechnology,2000,84:193-196.
[27]Sophie C,Russell J.Tweddell,J S,et al.Water activity control:a way to improve the efficiency of continuous lipase esterification.Biotechnology and Bioengineering,1998,60(3):362-368.
[28]周国伟,李干佐等.不同微乳液体系和微乳液凝胶中的酶催化反应。日用化学工业,2001,3:35-39.
[29]宋少芳,栾玉霞.微乳液凝胶固定化脂肪酶催化α-单硬脂酸甘油酯水解反应活性.应用化学,2006,23(2):188-192.
[30]Francesco Lopez,Andrea Ceglie,et al.The novel hexadecyltrimethylammonium bromide(CTAB)based organogel as reactor for ester synthesis by entrapped Candida rugosa lipase.Process Biochemistry,2006,41:114-119.
[31]M.Zoumpanioti,M.Karali,et al.Lipase biocatalytic processes in surfactant free microemulsion-like ternary systems and related organogels.Enzyme and Microbial Technology,2006,39:531-539.
[32]Nakamura,K.,Chi,Y.M.,et al.Lipase activity and stability in supercritical carbon dioxide. Chemical Engineering Communications,1985,45:207-212.
[33]Novotny,M.,Bertsch,W.,et al.Temperature and pressure effects in supercritical-fluid chromatography.Journal of Chromatography,1971,61:17-28.
[34]Chiara Giulia Laudani,Maja Habulin,et al.Immobilized lipase-mediated long-chain fatty acid esterification in dense carbon dioxide:bench-scale packed-bed reactor study.J.of Supercritical Fluids,2006,10-16.
[35]Randolph,T.W.,Blanch,H.W.,et al.Enzyme catalyzed oxidation of cholesterol in supercritical carbon dioxide.AIChE Journal,1998,34:1354-1360.
[36]刘森林,宗敏华.超临界流体中酶催化的研究进展.微生物学通,2001,28(1):81-84.
[37]JAIN N,KUMAR A,et al.Chemical and biochemical transformations in ionic liquids.Tet rahedron.2005,61:1015-1060.
[38]KIM K W,SONGB,CHOI M Y,et al.Biocatalysis in ionic liquids:Markedly enhanced enantioselectivity of lipase.OrgLett,2001,3(10):1507-1509.
[39]NaraS J,MohileSS,Harjani J R,et al Influence of ionic liquids on the rates and regioselectivity of lipase-mediated biotransformations on 3,4,6-tri-O-acetyl-d-glucal.Mol.Catalysis B:Enzymatic,2004,28:39-43.
[40]Kim K W,Song B,et al.Biocatalysis in ionic liquids:markedly enhanced enantioselectivity of lipase.Org Lett,2001,3:1507-1509.
[41]蔡汉成,方云等.一种新的催化方法:微波辐射酶耦合催化有机合成.有机化学,2003,23(3):298-304.
[42]Akhila Rajan,V.S.Prasad,T.Emilia Abraham.Enzymatic esterification of starch using recovered coconut oil.International Journal of Biological Macromolecules,2006,39:265-272.
[43]Sapna Bradoo,Pooja Rathi,et al.Microwave-assisted rapid characterization of lipase selectivities.J.Biochem.Biophys.Methods,2002,51:115-120.
[44]Lin,G.L.;Lin,W.Y.Microwave-Promoted Lipase-Catalyzed Reactions.Tetrahedron Letters 1998,(39):4333-4336.
[45]Caldwell CG,Hills F,Wurzburg OB.United State Patent,2661349.1953.
[46]Randal L.Shogren,Arvind Viswanathan,et al.Distribution of Octenyl Succinate Groups in Octenyl Succinic Anhydride Modified Waxy Maize Starch.Starch,2000,52(4):196-204.
[47]Jeon Y.S,Viswanathan A,Gross R.A.Studies of starch esterification:reactions with alkenylsuccinates in aqueous slurry systems[J].Starch,1999,51(2):90-93.
[48]王骏涛,刘亚伟等.基于响应面法辛烯基琥珀酸淀粉酯制备的优化研究.粮油加工与食品机械,2006,2:83-89.
[49]Rajesh Bhosale,Rekha Singhal.Effect of octenylsuccinylation on physicochemical and functional properties of waxy maize and amaranth starches.Carbohydrate Polymers,2007,68:447-456.
[50]宋广勋,冯光炷.辛烯基琥珀酸淀粉酯的合成及其应用研究进展.粮油加工,2006,8:81-84.
[51]S.Hari Krishna,A.P.Sattur,N.G.Karanth,Lipae-catalyzed synthesis of isoamyl isobutyrate—optimization using a central composite rotatable design.Process Biochemistry,2001,37:9-16.
[52]Manuel Ferrera,Juan Soliverib,et al.Synthesis of sugar esters in solvent mixtures by lipases from Thermomyces lanuginosus and Candida antarctica B,and their antimicrobial properties.Enzyme and Microbial Technology,2005,36:391-398.
[53]马清仪,陈洪等.酶法合成月桂酸单甘油酯.过程工程学报,2004,4:36-42.
[54]Lei Qiao,Qu-Ming Gu,et al.Enzyme-catalyzed synthesis of hydrophobically modified starch,Carbohydrate Polymers,2006,66:135-140.
[55]Kuan-Ju Liu,Kuan-Miao Liu,Hung-Min Chang.Biocatalytic synthesis of paimitoyl vanillylamide in supercritical carbon dioxide through amidation of vanillylamine hydrochloride and palmitic anhydride by lipase.Food Chemistry,2007,102:1020-1026.
[56]YuanhongWang,RuiWang,Quanshun Li,Zuoming Zhang.Kinetic resolution of rac-alkyl alcohols via lipase-catalyzed enantioselective acylation using succinic anhydride as acylating agent.Journal of Molecular Catalysis B:Enzymatic,2008,02:1-4.
[57]Xiao Yan Wu,Sanna JEiskeliiinen,Yu-Yen Linko.An investigation of crude lipases for hydrolysis,esterification,and transesterification.Enzyme Microb.Technol.,1996,19:227-231.
[58]Jean Christophe Bellot,Luc Choisnard,et al.Combining solvent engineering and t hermodynamic modeling to enhance selectivity during monoglyceride synthesis by lipase-catalyzed esterification.Enzymeand MicrobialTechnology,2001,28:362-369.
[59]刘毅,杨连生.脂肪酶催化酯合成.食品科学,2001,22:88-90.
[60]G.V.Chowdary,S.G.Prapulla.The influence of water activity on the lipase catalyzed synthesis of butyl butyrate by transesterification.Process Biochemistry,2002,38:393-397.
[61]Eva M.K.Hedin,Karl Hult,et al.Low microwave-amplitude ESR spectroscopy:Measuring spin-relaxation interactions of moderately immobilized spin labels in proteins.J.Biochem.Biophys.Methods,2004(60):117-138.
[62]Ganapati D.Yadav,Piyush S.Lathi.Intensification of enzymatic synthesis of propylene glycol monolaurate from 1,2-propanedioi and lauric acid under microwave irradiation:Kinetics of forward and reverse reactions.Enzyme and Microbial Technology,2006(38):814-820.
[63]Ganapati D.Yadav,Piyush S.Lathi.Synergism between microwave and enzyme catalysis in intensification of reactions and selectivities:transesterification of methyl acetoacetate with alcohols.Journal of Molecular Catalysis A:Chemical,2004(223):51-56.
[64]Ganapati D.Yadav,Piyush S.Lathi.Intensification of enzymatic synthesis of propylene glycol monolaurate from 1,2-propanediol and lauric acid under microwave irradiation:Kinetics of forward and reverse reactions.Enzyme and Microbial Technology,2006,38:814-820.
[65]宋晓燕,阮晖等.糯玉米辛烯基琥珀酸淀粉酯的制备及其RVA谱特性分析.中国粮油学报,2006 26(1):55-60.
[66]卢时勇,钱俊青等.辛烯基琥珀酸淀粉酯的性能与合成方法.浙江化工,2004,35(2):15-17.
[67]H.L.Brockman.Triglyceride lipase from porcine pancreas.Methods Enzymol,1981,71:619-627.
[68]GUO-QING HE,XIAO-YAN SONG,et al.Octenyl Succinic Anhydride Modified Early Indica Rice Starches Differing in Amylose Content.Agric.Food Chem.2006,54:2775-2779.
[69]张友松.变性淀粉生产与应用手册北京,中国轻工业出版社,1999.
[70]高振江,吴薇.加热温度与马铃薯淀粉粒结构变化及食用口感的关系.食品科学,2003,4(24):27-30.
[71]Nidai Hilal,Viktor Kochkodan,et al.Lipase-immobilized biocatalytic membranes for enzymatic esterification:Comparison of various approaches to membrane preparation.Journal of Membrane Science,2006,268:198-207.
[72]沈德言.红外光谱在高分子中的应用.北京:科学出版社,1982.
[73]Sindhu Mathew,T.Emilia Abraham.Physico-chemical characterization of starch ferulates of different degrees of substitution.Food Chemistry,2007(105):579-589.
[74]Wang Y.J,Wang L.F.Characterization of acetylated waxy maize starches prepared under catalysis by different alkali and alkaline-earth hydroxides.Starch/Starke,2002,54:25-30.
[75]王秀艳,董丽松.变性淀粉结晶性和形态研究.中国粮油学报,2005,3(20):26-29.
[76]杨景峰,罗志刚等.粉晶体结构研究进展.食品工业科技,2004,07:240-243.
[77]Shogren,R.L.,Viswanathan,et al..Distribution of octenyl succinate groups in octenyl succinic anhydridemodified waxy maize starch.Starch/St(a|")rke,2000,52:196-204.
[78]Veronique G,Paul C,Brigitte B,et al.Structural Changesof Cassava Starch Granules after Heating at Intermediate WaterContents.Starch,1997,49(5):171-179.
[79]顾正彪.DSC在淀粉研究中的应用.无锡轻工大学学报,1996,15(2):179-182.
[80]Olayide S.Lawal.Succinyl and acetyl starch derivatives of a hybrid maize:physicochemical characteristics and retrogradationproperties monitored by differential scanning calorimetry.Carbohydrate Research,2004,339:2673-2682.
[81]宋晓燕.早籼米辛烯基琥珀酸淀粉酯的制备及其理化性质的研究.浙江大学博士学位论文.
[82]黄立新,高群玉等.酯化交联淀粉反应及性质的研究.食品与发酵工业,2001,27(6):1-5.
[83]郑桂富,徐振相等.羧甲基化对油莎豆淀粉糊性质改善的研究.食品工业科技,2002,27(7):27-29.
[84]卞希良,邬应龙等.琥珀酸糯米淀粉酯的制备以及性质的研究.粮油加工与食品机械,2006,3:88-91.
[85]许琼.辛烯基琥珀酸马铃薯淀粉酯的制备-性质及应用研究.浙江大学硕士学位论文
[86]Lawal O.S.Succinyl and acetyl starch derivatives of a hybrid maizes:physicochemical characteristics and retrogradation properties monitored by differential scanning calorimetry.Carbohyd.Res.2004,339:2673-2686.
[2]罗勤贵.变性淀粉的生产与应用现状.粮油加工,2006,6(31):50-53.
[3]卢时勇,钱俊青,邹小明等.辛烯基琥珀酸淀粉酯的性能与合成方法.浙江化工,2004,35(2):15-17.
[4]张友松.变性淀粉生产与应用手册.北京:中国轻工业出版社,1999.
[5]Xiaoyan Song,Guoqing He,et al.Preparation and Properties of Octenyl Succinic Anhydride Modified Early Indica Rice Starch.Starch/Staerke,2006,58:109-117.
[6]Atanu Biswas RL,Shogren S,et al.Rapid preparation of starch maleate half-esters.Carbohydrate Polymers,2006,64:484-487.
[7]陈均志,银鹏.微波有机相法制备辛烯基琥珀酸淀粉的研究.粮油食品科技,2004,12(1):16-18.
[8]Method of making lipophilic starch derivatives.Publication number:US4035235.1977-07-12.
[9]辛烯基琥珀酸酯淀粉生产新工艺.中国专利CN1563096,公开(公告)日:2005-01-12.
[10]Imitation cheese products containing modified starch as partial caseinate,replacement and method of preparation.Publication number:US4499116,1985-02-12.
[11]Arvind Viswanathanl.Effect of Degree of Substitution of Octenyl Succinate Starch on the mulsification Activity on Different Oil Phases.Journal of Environmental Polymer Degradation,1999,7:1991-1996.
[12]Rajesh Bhosale,Rekha Singhal.Process optimization for the synthesis of octenyl succinyl derivative of waxy corn and amaranth starches.Carbohydrate Polymers,2006,66:521-527.
[13]卞希良,邬应龙,夏凤清.琥珀酸糯米淀粉酯的制备以及性质的研究.粮油加工与食品机械2006,3:88-91
[14]Rudnik E,Matuschek G,Milanov N & Kettrup A.Thermal properties of starch succinates.Thermochimica Acta,2005,427:163-166.
[15]邓林伟,徐雪芬,袁长贵等.辛烯基琥珀酸淀粉酯(纯胶)的研制和应用研究.食品科技,2002,11:39-41.
[16]马春华,马兴胜.辛烯基琥珀酸淀粉酯在酸奶中的应用.乳业科学与技术,2006,2:68-69.
[17]张燕萍,郑茂强.辛烯基琥珀酸木薯淀粉酯在乳化桔子香精中的应用.无锡轻工大学学报,2004,23(5):74-77.
[18]李香春,甄宗国.脂肪酶特性及其应用.粮食与油脂,2003,3:19-20.
[19]Van Tilbeurg H,Sarda L,Verger R,et al.Structure of the pancreatic lipase procolipase complex.Nature,1992,359:159-162.
[20]魏纪平,熊宁波.固定化脂肪酶催化己酸乙酯的研究.广州食品工业科技,2003,19(1):15-17.
[21]Haas,Michael J.Fuels as solvents for the conduct of enzymatic reactions.US:5697986,1997.
[22]陈志锋,吴虹.固定化脂肪酶催化高酸废油脂酯交换生产生物柴油.催化学报,2006,27(2):146-150.
[23]Sasa Sabeder,Maja Habulin,Zeljko Knez.Lipase-catalyzed synthesis of fatty acid fructose esters.Journal of Molecular Catalysis B:Enzymatic,2006,43:58-62.
[24]Akhila Rajah,V.S.Prasad,T.Emilia Abraham.Enzymatic esterification of starch using recovered coconut oil.International Journal of Biological Macromolecules,2006,39:265-272.
[25]孙君社等.酶与酶工程及其应用.北京:化学工业出版社.
[26]Gbicza L,Kabiri B A,Keoves E,et al.Large-scale enzymatic production of natural flavour esters in organic solvent with continuous water removal.Journal of Biotechnology,2000,84:193-196.
[27]Sophie C,Russell J.Tweddell,J S,et al.Water activity control:a way to improve the efficiency of continuous lipase esterification.Biotechnology and Bioengineering,1998,60(3):362-368.
[28]周国伟,李干佐等.不同微乳液体系和微乳液凝胶中的酶催化反应。日用化学工业,2001,3:35-39.
[29]宋少芳,栾玉霞.微乳液凝胶固定化脂肪酶催化α-单硬脂酸甘油酯水解反应活性.应用化学,2006,23(2):188-192.
[30]Francesco Lopez,Andrea Ceglie,et al.The novel hexadecyltrimethylammonium bromide(CTAB)based organogel as reactor for ester synthesis by entrapped Candida rugosa lipase.Process Biochemistry,2006,41:114-119.
[31]M.Zoumpanioti,M.Karali,et al.Lipase biocatalytic processes in surfactant free microemulsion-like ternary systems and related organogels.Enzyme and Microbial Technology,2006,39:531-539.
[32]Nakamura,K.,Chi,Y.M.,et al.Lipase activity and stability in supercritical carbon dioxide. Chemical Engineering Communications,1985,45:207-212.
[33]Novotny,M.,Bertsch,W.,et al.Temperature and pressure effects in supercritical-fluid chromatography.Journal of Chromatography,1971,61:17-28.
[34]Chiara Giulia Laudani,Maja Habulin,et al.Immobilized lipase-mediated long-chain fatty acid esterification in dense carbon dioxide:bench-scale packed-bed reactor study.J.of Supercritical Fluids,2006,10-16.
[35]Randolph,T.W.,Blanch,H.W.,et al.Enzyme catalyzed oxidation of cholesterol in supercritical carbon dioxide.AIChE Journal,1998,34:1354-1360.
[36]刘森林,宗敏华.超临界流体中酶催化的研究进展.微生物学通,2001,28(1):81-84.
[37]JAIN N,KUMAR A,et al.Chemical and biochemical transformations in ionic liquids.Tet rahedron.2005,61:1015-1060.
[38]KIM K W,SONGB,CHOI M Y,et al.Biocatalysis in ionic liquids:Markedly enhanced enantioselectivity of lipase.OrgLett,2001,3(10):1507-1509.
[39]NaraS J,MohileSS,Harjani J R,et al Influence of ionic liquids on the rates and regioselectivity of lipase-mediated biotransformations on 3,4,6-tri-O-acetyl-d-glucal.Mol.Catalysis B:Enzymatic,2004,28:39-43.
[40]Kim K W,Song B,et al.Biocatalysis in ionic liquids:markedly enhanced enantioselectivity of lipase.Org Lett,2001,3:1507-1509.
[41]蔡汉成,方云等.一种新的催化方法:微波辐射酶耦合催化有机合成.有机化学,2003,23(3):298-304.
[42]Akhila Rajan,V.S.Prasad,T.Emilia Abraham.Enzymatic esterification of starch using recovered coconut oil.International Journal of Biological Macromolecules,2006,39:265-272.
[43]Sapna Bradoo,Pooja Rathi,et al.Microwave-assisted rapid characterization of lipase selectivities.J.Biochem.Biophys.Methods,2002,51:115-120.
[44]Lin,G.L.;Lin,W.Y.Microwave-Promoted Lipase-Catalyzed Reactions.Tetrahedron Letters 1998,(39):4333-4336.
[45]Caldwell CG,Hills F,Wurzburg OB.United State Patent,2661349.1953.
[46]Randal L.Shogren,Arvind Viswanathan,et al.Distribution of Octenyl Succinate Groups in Octenyl Succinic Anhydride Modified Waxy Maize Starch.Starch,2000,52(4):196-204.
[47]Jeon Y.S,Viswanathan A,Gross R.A.Studies of starch esterification:reactions with alkenylsuccinates in aqueous slurry systems[J].Starch,1999,51(2):90-93.
[48]王骏涛,刘亚伟等.基于响应面法辛烯基琥珀酸淀粉酯制备的优化研究.粮油加工与食品机械,2006,2:83-89.
[49]Rajesh Bhosale,Rekha Singhal.Effect of octenylsuccinylation on physicochemical and functional properties of waxy maize and amaranth starches.Carbohydrate Polymers,2007,68:447-456.
[50]宋广勋,冯光炷.辛烯基琥珀酸淀粉酯的合成及其应用研究进展.粮油加工,2006,8:81-84.
[51]S.Hari Krishna,A.P.Sattur,N.G.Karanth,Lipae-catalyzed synthesis of isoamyl isobutyrate—optimization using a central composite rotatable design.Process Biochemistry,2001,37:9-16.
[52]Manuel Ferrera,Juan Soliverib,et al.Synthesis of sugar esters in solvent mixtures by lipases from Thermomyces lanuginosus and Candida antarctica B,and their antimicrobial properties.Enzyme and Microbial Technology,2005,36:391-398.
[53]马清仪,陈洪等.酶法合成月桂酸单甘油酯.过程工程学报,2004,4:36-42.
[54]Lei Qiao,Qu-Ming Gu,et al.Enzyme-catalyzed synthesis of hydrophobically modified starch,Carbohydrate Polymers,2006,66:135-140.
[55]Kuan-Ju Liu,Kuan-Miao Liu,Hung-Min Chang.Biocatalytic synthesis of paimitoyl vanillylamide in supercritical carbon dioxide through amidation of vanillylamine hydrochloride and palmitic anhydride by lipase.Food Chemistry,2007,102:1020-1026.
[56]YuanhongWang,RuiWang,Quanshun Li,Zuoming Zhang.Kinetic resolution of rac-alkyl alcohols via lipase-catalyzed enantioselective acylation using succinic anhydride as acylating agent.Journal of Molecular Catalysis B:Enzymatic,2008,02:1-4.
[57]Xiao Yan Wu,Sanna JEiskeliiinen,Yu-Yen Linko.An investigation of crude lipases for hydrolysis,esterification,and transesterification.Enzyme Microb.Technol.,1996,19:227-231.
[58]Jean Christophe Bellot,Luc Choisnard,et al.Combining solvent engineering and t hermodynamic modeling to enhance selectivity during monoglyceride synthesis by lipase-catalyzed esterification.Enzymeand MicrobialTechnology,2001,28:362-369.
[59]刘毅,杨连生.脂肪酶催化酯合成.食品科学,2001,22:88-90.
[60]G.V.Chowdary,S.G.Prapulla.The influence of water activity on the lipase catalyzed synthesis of butyl butyrate by transesterification.Process Biochemistry,2002,38:393-397.
[61]Eva M.K.Hedin,Karl Hult,et al.Low microwave-amplitude ESR spectroscopy:Measuring spin-relaxation interactions of moderately immobilized spin labels in proteins.J.Biochem.Biophys.Methods,2004(60):117-138.
[62]Ganapati D.Yadav,Piyush S.Lathi.Intensification of enzymatic synthesis of propylene glycol monolaurate from 1,2-propanedioi and lauric acid under microwave irradiation:Kinetics of forward and reverse reactions.Enzyme and Microbial Technology,2006(38):814-820.
[63]Ganapati D.Yadav,Piyush S.Lathi.Synergism between microwave and enzyme catalysis in intensification of reactions and selectivities:transesterification of methyl acetoacetate with alcohols.Journal of Molecular Catalysis A:Chemical,2004(223):51-56.
[64]Ganapati D.Yadav,Piyush S.Lathi.Intensification of enzymatic synthesis of propylene glycol monolaurate from 1,2-propanediol and lauric acid under microwave irradiation:Kinetics of forward and reverse reactions.Enzyme and Microbial Technology,2006,38:814-820.
[65]宋晓燕,阮晖等.糯玉米辛烯基琥珀酸淀粉酯的制备及其RVA谱特性分析.中国粮油学报,2006 26(1):55-60.
[66]卢时勇,钱俊青等.辛烯基琥珀酸淀粉酯的性能与合成方法.浙江化工,2004,35(2):15-17.
[67]H.L.Brockman.Triglyceride lipase from porcine pancreas.Methods Enzymol,1981,71:619-627.
[68]GUO-QING HE,XIAO-YAN SONG,et al.Octenyl Succinic Anhydride Modified Early Indica Rice Starches Differing in Amylose Content.Agric.Food Chem.2006,54:2775-2779.
[69]张友松.变性淀粉生产与应用手册北京,中国轻工业出版社,1999.
[70]高振江,吴薇.加热温度与马铃薯淀粉粒结构变化及食用口感的关系.食品科学,2003,4(24):27-30.
[71]Nidai Hilal,Viktor Kochkodan,et al.Lipase-immobilized biocatalytic membranes for enzymatic esterification:Comparison of various approaches to membrane preparation.Journal of Membrane Science,2006,268:198-207.
[72]沈德言.红外光谱在高分子中的应用.北京:科学出版社,1982.
[73]Sindhu Mathew,T.Emilia Abraham.Physico-chemical characterization of starch ferulates of different degrees of substitution.Food Chemistry,2007(105):579-589.
[74]Wang Y.J,Wang L.F.Characterization of acetylated waxy maize starches prepared under catalysis by different alkali and alkaline-earth hydroxides.Starch/Starke,2002,54:25-30.
[75]王秀艳,董丽松.变性淀粉结晶性和形态研究.中国粮油学报,2005,3(20):26-29.
[76]杨景峰,罗志刚等.粉晶体结构研究进展.食品工业科技,2004,07:240-243.
[77]Shogren,R.L.,Viswanathan,et al..Distribution of octenyl succinate groups in octenyl succinic anhydridemodified waxy maize starch.Starch/St(a|")rke,2000,52:196-204.
[78]Veronique G,Paul C,Brigitte B,et al.Structural Changesof Cassava Starch Granules after Heating at Intermediate WaterContents.Starch,1997,49(5):171-179.
[79]顾正彪.DSC在淀粉研究中的应用.无锡轻工大学学报,1996,15(2):179-182.
[80]Olayide S.Lawal.Succinyl and acetyl starch derivatives of a hybrid maize:physicochemical characteristics and retrogradationproperties monitored by differential scanning calorimetry.Carbohydrate Research,2004,339:2673-2682.
[81]宋晓燕.早籼米辛烯基琥珀酸淀粉酯的制备及其理化性质的研究.浙江大学博士学位论文.
[82]黄立新,高群玉等.酯化交联淀粉反应及性质的研究.食品与发酵工业,2001,27(6):1-5.
[83]郑桂富,徐振相等.羧甲基化对油莎豆淀粉糊性质改善的研究.食品工业科技,2002,27(7):27-29.
[84]卞希良,邬应龙等.琥珀酸糯米淀粉酯的制备以及性质的研究.粮油加工与食品机械,2006,3:88-91.
[85]许琼.辛烯基琥珀酸马铃薯淀粉酯的制备-性质及应用研究.浙江大学硕士学位论文
[86]Lawal O.S.Succinyl and acetyl starch derivatives of a hybrid maizes:physicochemical characteristics and retrogradation properties monitored by differential scanning calorimetry.Carbohyd.Res.2004,339:2673-2686.