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240 W,月桂酸用量为30%,酶加入量为7%,反应时间26 min.     

高取代淀粉磷酸单酯合成的研究

本文对木薯淀粉干法酯化中淀粉乳液的浓度、pH值、Na_2HPO_4和NaH_2PO_4的用量对酯化取代度的影响,并对酯化温度,反应时间、催化剂用量与取代度、粘度的关系作了探讨,确定了合成高取代淀粉磷酸单酯的最佳反应条件。     

无溶剂体系中酶促合成糖酯

以固定在阴离子树脂上的脂肪酶Novozym435为催化剂,在无溶剂体系中研究了果糖与月桂酸的直接酯化反应.对反应条件进行了优化,在加水量30μL、pH值7.5、月桂酸与果糖摩尔比5∶1、加酶量与底物质量比17%、温度为60℃、反应48 h,达到最大相对转化率为75.6%(以果糖月桂酸双酯计算),比不加水时的49.2%有了较大的提高.产物经TLC分析,果糖月桂酸单酯Rf值为0.44,果糖月桂酸双酯Rf值为0.79,13C NMR鉴定,产物主要是1-β-D-呋喃果糖月桂酸单酯和1,6-β-D呋喃果糖月桂酸双酯.与传统有溶剂反应相比,无溶剂反应更易于后期分离纯化,并节省了溶剂,降低了生产成本.     

脂肪酶催化一步酯化协同拆分合成S-萘普生淀粉酯前药

利用CRL脂肪酶选择性催化外消旋萘普生甲酯与玉米淀粉进行转酯化反应合成光学纯S-萘普生淀粉酯前药,同时达到拆分外消旋萘普生的目的。考察了有机溶剂、脂肪酶用量、底物浓度比、反应温度对酯化协同拆分反应的影响,结果表明在异辛烷中脂肪酶CRL可以催化S-萘普生甲酯与淀粉发生转酯化反应同时完成外消旋萘普生的拆分,并且在脂肪酶用量为10%、底物浓度比为1:3、异辛烷用量为15mL、反应温度为60℃的条件下反应6d,外消旋萘普生甲酯的转化率为27.2%,产物对应体过量值eep高达99.4%可以作为萘普生的前药进行应用。     

混合溶剂中酶促合成维生素A乳酸酯

研究了混合溶剂中脂肪酶催化合成维生素A乳酸酯.首先对催化合成维生素A乳酸酯反应的脂肪酶和反应介质进行了研究,其次对影响合成维生素A乳酸酯反应的因素(温度、底物摩尔比、反应时间和酶量等)进行了探讨,优化了反应条件:在5 mL混合溶剂(叔丁醇/正己烷(v/v)=3:2)中,0.167 g维生素A醋酸酯和0.150g乳酸在25 mg脂肪酶Novozym 435催化下,在35℃、150 r/m in下反应6 h,产率可以达到52.19%,固定化酶可连续使用5次以上,产率仍达45%以上.     

有机相中脂肪酶催化合成乳酸乙酯

 考察了在双底物抑制下脂肪酶催化合成乳酸乙酯,最佳溶剂为叔丁醇,在所选的几种脂肪酶中,固定化于大孔丙烯酸树脂的南极假丝酵母脂肪酶B (Novozym 435)的催化活性最好. 对反应条件进行了优化,当酸醇摩尔比为1∶8, 反应温度60 ℃, 酸浓度0.3 mol/L, 酶浓度45 g/mol, 摇床转速200 r/min时产率达到77%, 脂肪酶Novozym 435重复使用6次后产率仍然可达到60%.     

脂肪酶催化一步酯化协同拆分合成S-萘普生淀粉酯

利用CRL脂肪酶选择性催化外消旋萘普生甲酯与玉米淀粉进行转酯化反应合成光学纯S-萘普生淀粉酯,同时达到拆分外消旋萘普生的目的.考察了有机溶剂、脂肪酶用量、底物浓度比、反应温度对酯化协同拆分反应的影响,结果表明在异辛烷中脂肪酶CRL可以催化S-萘普生甲酯与淀粉发生转酯化反应同时完成外消旋萘普生的拆分,并且在脂肪酶用量为10%、底物浓度比为1∶3、异辛烷用量为15 m L、反应温度为60℃的条件下反应6d,外消旋萘普生甲酯的转化率为42.5%,产物对映体过量值eep高达99.1%.     

有机相中α-氰基-3-苯氧基苄醇乙酯的酶促醇解反应

研究了有机相中脂肪酶催化α-氰基-3-苯氧基苄醇乙酯的醇解化反应。制备α -氰基-3-苯氧基苄醇。考察了酶、溶剂、醇、醇用量、溶剂水含量以及底物浓度等 因素对反应的影响，结果表明Novozym435脂肪酶催化活性最高，经实验确定的最佳 条件为：脱水甲苯为溶剂，正辛醇为酰基受体，正辛醇、酯的摩尔比为1.5:1，酶 量为8 mg/mL时的最佳底物浓度为108.13 mmol/L，在上述条件下反应30 h酯的转化 率 > 96%。     

脂肪酶催化缩聚法合成可完全降解的聚羟基丙酸酯(英文)

以3-羟基丙酸甲酯为聚合单体,建立了以固定化脂肪酶Novozym 435为催化剂的酶催化缩聚反应体系,合成可完全降解的高分子聚酯聚羟基丙酸酯,考察了反应条件和介质对反应性能的影响,结果表明,纯度大于95%的单体即可在温和条件下合成聚羟基羧酸酯;降低反应压力可有效提升产物产率和分子量.通过选择合适的有机溶剂介质和表面活性剂,可使产物分子量提升至13000(Mw)以上.脂肪酶催化剂重复利用能力优异,经6批次反应后,其相对活性保持在95%以上.     

干法制备阳离子淀粉(I):反应效率的研究

在碱催化剂BZ-1存在下,以N-(2,3-环氧丙基)三甲基氯化铵(GTA)为阳离子化试剂,干法制备了高取代度季铵型阳离子淀粉.考察了碱催化剂BZ-1、水含量、反应温度和反应时间对取代度和反应效率的影响.当淀粉用量为5.5g,GTA用量为3g时,最佳反应条件为:碱催化剂BZ-1 0.8g、反应温度60℃、反应时间4h、反应体系含水量24%,取代度可达0.56,反应效率为88%.     

Thermal stability and degradation of starch derivatives

Thermal behaviour of different starch derivatives, i.e. starch esters and ethers having degree of substitution (DS) in the range of 0.02–0.18 were studied. Potato, maize and wheat starches were used. Measurements were carried out by coupled thermal analysis/ mass spectrometry method (STA-MS) in air atmosphere. The major DTG peak during the investigation for starch derivatives is observed below 300°C. The mass loss up to a temperature of 300°C is about 50%. The most abundant ions found areH₂O⁺ and CO₂ ⁺. For the studied starch derivatives with a low degree of substitution (DS<0.18) no correlation was found between thermal stability and the level of substitution regardless of the nature of substitution.     

Starch Formates: Synthesis and Modification

Starch can be efficiently converted into the corresponding formates homogeneously using N-formyl imidazole obtained by the reaction of 1,1′-carbonyldiimidazole and formic acid in dimethyl sulfoxide as a solvent. Starch formates are soluble in polar aprotic solvents, not susceptible against hydrolysis, and not meltable. Thermoplastics could be generated by conversion of starch formates with long-chain fatty acids exemplified by the conversion with lauroyl chloride in N,N-dimethylacetamide, leading to mixed starch laurate formates. The mixed esters show melting temperatures mainly dependent on the amount of laurate ester moieties.     

乙酰化淀粉的塑化和性能研究

以乙酰化改性淀粉为基体,甘油为增塑剂,利用哈克旋转流变仪密炼制备热塑性乙酰化淀粉.实验结果表明制备热塑性乙酰化淀粉的甘油/乙酰化淀粉配比应大于30/100(W/W),且随甘油含量增加,热塑性乙酰化淀粉的脆性降低.动态机械热分析(DMTA)显示热塑性乙酰化淀粉包含富甘油和富淀粉两相,乙酰化淀粉和甘油为部分互溶.流变学分析显示淀粉分子间作用力非常强,表现为类固态行为.同时本文对材料的热稳定性进行了初步研究.     

Starch Granule Size and Morphology of Arabidopsis thaliana Starch-Related Mutants Analyzed during Diurnal Rhythm and Development

Transitory starch plays a central role in the life cycle of plants. Many aspects of this important metabolism remain unknown; however, starch granules provide insight into this persistent metabolic process. Therefore, monitoring alterations in starch granules with high temporal resolution provides one significant avenue to improve understanding. Here, a previously established method that combines LCSM and safranin-O staining for in vivo imaging of transitory starch granules in leaves of Arabidopsis thaliana was employed to demonstrate, for the first time, the alterations in starch granule size and morphology that occur both throughout the day and during leaf aging. Several starch-related mutants were included, which revealed differences among the generated granules. In ptst2 and sex1-8, the starch granules in old leaves were much larger than those in young leaves; however, the typical flattened discoid morphology was maintained. In ss4 and dpe2/phs1/ss4, the morphology of starch granules in young leaves was altered, with a more rounded shape observed. With leaf development, the starch granules became spherical exclusively in dpe2/phs1/ss4. Thus, the presented data provide new insights to contribute to the understanding of starch granule morphogenesis.     

酶法制备微孔淀粉的研究进展

微孔淀粉是淀粉酶在低于淀粉糊化温度下水解生淀粉形成的一种新型变性淀粉.本文综述了酶法制备微孔淀粉的一些相关影响因素,并探讨了酶法制备微孔淀粉的基本研究成果和进展,以及酶法淀粉微孔化技术的前景展望.     

Thermal transitions of cassava starch at intermediate water contents

Order-disorder transitions were investigated in native cassava starch at intermediate moisture contents (35 to 60% wt. water), using Differential Scanning Calorimetry (DSC) and dynamic Wide Angle X-ray Diffractometry (WAXS) with a synchrotron radiation source.The gelatinization of granules occurs as a cooperative process, due to constraints induced in crystallites by the amorphous areas. Variations of water content (water volume fraction from 0.28 to 0.86) and heating rate (0.2–10C min^–1) allowed access to equilibrium melting conditions. Cassava starch exhibits a higher melting temperature of the undiluted starch (T _m ^o ) and an equivalent melting enthalpy of the repeating glucosyl unit (H _u), compared to other A-type starches. At intermediate water content (45% wt. water), a two-stage melting process is evidenced, with different kinetic rates below and above 75 C.We wish to thank F. Lavigne (URA, CNRS 1218, Chatenay Malabry) for valuable help with this work and C. Bourgaux from L.U.R.E. for helping us with dynamic X-ray diffraction experiments. The present study was supported by a grant from the European Communities (STD3-CT92-0110).     

高温下淀粉凝胶化颗粒的结构特征

凝胶化作用是淀粉改性过程中存在的一种现象。采用红外光谱和X-射线衍射方法探讨了淀粉凝胶化颗粒的结构和结晶变化过程。结果表明,在淀粉的高温成型过程中,凝胶化颗粒化学结构没有发生明显的变化,结晶状态则趋于完全无定型化。     

Synthesis and Properties of Novel Hydrogels from Cross-linked Starch Phosphates

Summary: Starch based stable hydrogels providing high swelling and water storing capacity are not only of certain interest for the cosmetics and hygiene industry but also have the potential to become an effective tool in combating desertification and supporting cultivation in many regions of the world. It has been found that strong water adsorbing covalent networks with free swelling capacity (FSC) of up to 190 g water/g hydrogel can be obtained by cross-linking low-substituted mono-starch phosphates (MSP) in a semi-dry process with di- and tricarboxylic acids such as succinic acid (SA), adipic acid (AA) or citric acid (CA). The linear behaviour over a wide frequency range of the rheological parameters G′ and G″ which were determined by using a shearing disc viscosimeter clearly reveal that the cross-linked starch phosphates are stable hydrogels having stronger elastic than viscous properties.     

Production of Cyclodextrins by CGTase from Bacillus clausii Using Different Starches as Substrates

Cyclodextrins (CDs) are cyclic oligasaccharides composed by d-glucose monomers joined by α-1,4-d glicosidic linkages. The main types of CDs are α-, β- and γ-CDs consisting of cycles of six, seven, and eight glucose monomers, respectively. Their ability to form inclusion complexes is the most important characteristic, allowing their wide industrial application. The physical property of the CD-complexed compound can be altered to improve stability, volatility, solubility, or bio-availability. The cyclomaltodextrin glucanotransferase (CGTase, EC 2.4.1.19) is an enzyme capable of converting starch into CD molecules. In this work, the CGTase produced by Bacillus clausii strain E16 was used to produce CD from maltodextrin and different starches (commercial soluble starch, corn, cassava, sweet potato, and waxy corn starches) as substrates. It was observed that the substrate sources influence the kind of CD obtained and that this CGTase displays a β-CGTase action, presenting a better conversion of soluble starch at 1.0%, of which 80% was converted in CDs. The ratio of total CD produced was 0:0.89:0.11 for α/β/γ. It was also observed that root and tuber starches were more accessible to CGTase action than seed starch under the studied conditions.     

热塑性淀粉力学性能的提升途径及作用机理

以可再生资源(如淀粉、纤维素和蛋白质等)为基础发展而来的生物可降解塑料受到人们越来越多的关注,是可降解塑料行业发展的重要方向之一。天然淀粉由于来源广、低成本和可生物降解的特点,广泛用于制备淀粉塑料,并用于农业、食品、医药和包装等行业,有望取代石油基衍生聚合物。淀粉大分子具有结晶结构,所含大量羟基可形成较强的分子间和分子内氢键,使其不能热塑加工,而当加入增塑剂后可破坏其结晶结构,从而用于制备热塑性淀粉。目前,热塑性淀粉的力学性能差,是影响其使用性能的首要问题。近年来国内外开展了大量的研究以试图增强其力学性能。本文主要以不同类型的热塑性淀粉为基础,以淀粉自身改性和外加组分改性两种提高其力学性能的途径为主线,以其力学性能的提升方法和作用机理为重点,系统总结了近年来国内外以提高热塑性淀粉材料的力学性能为目的的研究工作,归纳了影响力学性能的相关因素以及提升途径,并对该领域重点研究的内容进行了总结和展望。