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。     

球磨处理对豌豆淀粉结构及理化性质的影响

为探究球磨研磨处理对豌豆淀粉结构及性质的影响,采用扫描电镜、激光粒度分析仪、X-射线衍射仪、傅立叶红外光谱仪、差示扫描量热仪、快速黏度分析仪等分析手段研究经研磨处理后豌豆淀粉颗粒形貌、晶体结构和理化性质。结果表明,淀粉颗粒形貌由光滑的多角形变为表面粗糙的不规则形状,处理后豌豆淀粉粒度增大,粒度中位径达到23.28μm,偏光十字消失;淀粉颗粒结晶结构被破坏,由多晶态向无定形态转变,呈现非晶化状态;研磨过程淀粉无新的基团产生,淀粉颗粒由有序结构向无序化结构转变;热焓值、糊化温度均显著降低,热糊稳定性好,处理后豌豆淀粉具有较好的热糊稳定性和冷糊力学稳定性。     

高温下淀粉的凝胶化作用

凝胶化作用是淀粉及改性产品生产过程中存在的一种现象。淀粉凝胶化作用的结果导致了在其产品中产生了只溶胀但不溶解的颗粒,从而影响了淀粉产品的整体性能。文章初步探讨了淀粉在高温成型过程中凝胶化作用的方式和起因。结果表明,淀粉浆料在高温成型过程中所产生的凝胶团粒是淀粉不完整的凝胶化作用的结果,足量的水分和高温是形成较多的凝胶化淀粉颗粒的原因。     

单模聚焦微波辅助合成1-乙基-3-羧甲基咪唑四氟硼酸盐离子液体

以1-乙基咪唑为原料,采用discover环形单模聚焦微波合成仪合成了1-乙基-3-羧甲基咪唑四氟硼酸盐离子液体,对产品结构进行了表征及热性分析,并测定了粘度、密度、表面张力、电化学窗口等物化性能,同时考察了合成离子液体对淀粉的溶解性能.结果表明,单模聚焦微波辐射合成具有速度快、时间短、反应条件温和等优点,产品产率为88.23％,其密度、粘度、表面张力与温度均呈线性关系,且随温度升高而减小.与水溶剂相比,合成的离子液体对可溶性淀粉具有较高的溶解度,为淀粉及其衍生物的均相衍生化反应提供了理论基础.     

草酸淀粉酯制备及其性能研究

本文以草酸和玉米淀粉为原料,通过改变原料的摩尔比反应制备了不同取代度(0.1到0.9)的草酸淀粉酯,采用滴定法测定产物的取代度,利用红外光谱和核磁共振表征产物(取代度为0.41)的化学结构,产物中含有羰基的结果表明成功制备了草酸淀粉酯.详细考察了草酸淀粉酯的物理化学性质,利用粘度测定、热重分析、广角X衍射(WXRD)以及湿度吸收等研究不同取代度的草酸淀粉酯的分子量、热稳定性,结晶形态以及吸水性能.结果说明,与玉米淀粉相比,草酸淀粉酯的吸水率随着取代度的提高而增加,其分子量、热稳定性以及结晶性能则呈下降趋势.     

蔗糖酯和尿素对淀粉改性的协效作用

蔗糖酯是一种对环境无害的表面活性剂,含有与淀粉相容的极性头.将不同比例蔗糖硬脂酸酯加入到玉米淀粉或20％尿素增塑的玉米淀粉中,在热水中煮浆后浇铸成膜.采用X-射线衍射法表征淀粉膜的结晶结构,并测定了浆膜在不同相对湿度下的吸湿性以及浆膜的拉伸性能.结果表明,蔗糖酯可与淀粉形成V-型包合配合物,并影响淀粉的B-型结晶,因此改变淀粉的吸湿性和力学性能.添加0.5％蔗糖酯使淀粉的吸湿率提高,随着蔗糖酯进一步增加,淀粉的吸湿率下降.含尿素20％的淀粉混合物中添加不同比例的蔗糖酯,对淀粉材料的结晶度、结晶形态,以及吸湿率和力学性能产生了不同的影响.蔗糖酯与尿素对淀粉材料改性具有协效作用.含蔗糖酯0.5％的尿素增塑淀粉膜显示出非晶特征,且具有较高的断裂伸长.     

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。     

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.     

《化学通报》网络版2003年第5期论文摘要

[Ｗ 0 3 2 ]ＤＳＣ分析方法在淀粉凝胶化研究中的应用ＡｐｐｌｉｃａｔｉｏｎｏｆＤＳＣｉｎＳｔｕｄｙｏｆＳｔａｒｃｈＧｅｌａｔｉｎｉｚａｔｉｏｎ孙秀萍　于九皋 　刘延奇 (天津大学理学院化学系　天津　 3 0 0 0 72 )综述了近年来ＤＳＣ技术在淀粉热力学性质特别是淀粉凝胶化性质研究中的重要贡献及与凝胶化相关的一些问题。分别介绍了直链淀粉含量、盐的种类和浓度及体系湿含量对淀粉凝胶化性质的影响 ,描述了淀粉凝胶化作用机制 ,并对利用ＤＳＣ曲线预测淀粉、淀粉 水体系结构特性的方法进行了探讨。Ｔｈｅａｐｐｌｉｃａｔｉｏｎ…     

离子液体增塑改性玉米淀粉/聚丁二酸丁二醇酯共混材料的结构与性能

为考察离子液体对淀粉/聚丁二酸丁二醇酯(PBS)的作用效果,降低淀粉/PBS的脆性,以离子液体(1-丁基-3-甲基咪唑氯盐[BMIM]Cl)作为增塑改性剂通过熔融共混法制备了玉米淀粉/聚丁二酸丁二醇酯(PBS)共混材料,采用红外光谱(FTIR)、扫描电镜(SEM)、热重分析(TGA)、X射线衍射分析(XRD)及力学性能测试方法研究了[BMIM]Cl对淀粉/PBS共混材料结构和性能的影响.结果表明,[BMIM]Cl能与淀粉/PBS分子发生强相互作用,破坏淀粉/PBS共混物中原有的氢键与结晶结构,增强界面相互作用,改善相容性,进而改变淀粉/PBS共混材料的结构与性能;[BMIM]Cl的加入不影响淀粉/PBS的热稳定性,可使材料玻璃化转变温度(Tg)、结晶温度(Tc)、冷结晶温度(Tcc)及结晶度(Xc)降低.[BMIM]Cl具有显著降低淀粉/PBS脆性的作用,使其断裂伸长率大幅度增加,拉伸强度和弹性模量降低.     

淀粉与丙烯酰胺流变相的微波辐射接枝共聚

微波辐射淀粉接枝乙烯基类单体的共聚反应，一般都采用溶液聚合，得到的产物含水量大，产物分离困难。本文将流变相反应法用于接枝共聚反应，探讨微波辐射下玉米淀粉与丙烯酰胺流变相态接枝共聚反应。     

"微波固相法"合成羧甲基淀粉及其助洗性能的研究

羧甲基淀粉(CMS)是一种重要的淀粉衍生物，在医药、食品、纺织、印染、洗涤剂、印刷、造纸、冶金、石油钻井等方面有广泛用途。CMS的合成方法有传统的水媒法、溶媒法以及固相法。这些方法各有优缺点：水媒法一般不能生产取代度大于0．1的产品，溶媒法则需要大量有机溶剂，生产成本较高，而且它们都需要较长的反应时间，固相法反应受热不均匀。为此采用微波固相法合成CMS，同时，研究了产品的助洗性能，并与溶媒法比较，结果基本一致。     

氧化铅@碳纳米复合材料的制备与表征

以淀粉为碳源, 高温碳化含有硝酸铅的淀粉干凝胶, 制备了氧化铅@碳纳米复合材料,氧化铅颗粒无团聚, 粒径可调, 近于单分散, 且分布均匀, 可作为铅酸电池的电极材料, 有望提高其充放电性能和使用寿命.     

Tailoring the properties of thermoplastic starch by blending with cinnamyl alcohol and radiation processing: An insight into the competitive grafting and scission reactions

The present paper focuses on the effects of electron beam (EB) irradiation on thermoplastic materials based on destructurized starch including glycerol and water as plasticizers to assess the potentiality of cinnamyl alcohol as reactive additive capable of counterbalancing the degradation of the polysaccharide by inducing interchain covalent linkages. The tensile properties at break of test specimens of controlled composition submitted to EB irradiation at doses ranging from 50 to 200 kGy revealed the presence of competitive chain scission and bridging in samples containing cinnamyl alcohol at a relative concentration of 2.5% with regard to dry starch. The occurrence of crosslinking under particular conditions was evidenced by gel fraction measurements. The treatment under radiation was also applied to model blends including maltodextrin as a model for starch and the other ingredients to gain an insight into the radiation induced mechanisms at the molecular level. The presence of cinnamyl alcohol is found to limit degradation. Size exclusion chromatography and gel fraction allowed to monitor the effects and confirmed unambiguously the attachment of UV-absorbing chromophores onto the maltodextrin main chain. The combination of the obtained results demonstrates the possibility of altering in a favorable way the tensile properties of plasticized starch by applying high energy radiation to properly formulated blends including aromatic compounds like cinnamyl alcohol.     

Characterization of Starch/Acrylic Acid Super‐Absorbent Hydrogels Prepared by Ionizing Radiation

Copolymerization of acrylic acid (AAc) and gelatinized maize starch in aqueous medium using γ‐irradiation, followed by neutralization with alkali solution was carried out. The preparation conditions, such as irradiation dose and starch/AAc compositions were investigated. The higher the irradiation dose, as well as the AAc content in the feed solution, the higher the gel content. The copolymers were characterized by FTIR spectroscopy, thermo‐gravimetric analysis (TGA) and scanning electron microscopy (SEM). SEM revealed that the higher the dose, the lower the copolymer pore size. Starch/AAc copolymers have thermal stability higher than that for starch and poly acrylic acid individually. The swelling of starch/AAc hydrogels reduced as the gel content increases. The maximum water absorption obtained for starch/AAc hydrogels in distilled water was 200 g/g, and for neutralized starch/AAc hydrogels was 350 g/g. The swelling ratio of starch/AAc hydrogels of different compositions in NaCl solution is lower than that obtained in distilled water. The results suggest that the neutralized starch/AAc hydrogels have a high swelling property, and can be used in a variety of commercial applications.     

Effects of radiation on frozen lactate dehydrogenase

Results concerning the influence of 6-MeV electron beam irradiation, of 2.45-GHz, 565-W microwaves, and of the combined electron and microwave irradiation, at -21 degrees C and -196 degrees C, on lactate dehydrogenase activity are presented. The microwave-irradiated samples exhibited a non-linear behaviour (successive activation and inactivation of the enzyme molecules), suggesting the major influence of the non-thermal component of microwave radiation. The combined electron and microwave irradiation led to a decrease of activity similar to the one caused by electron beam irradiation, which seemed to prove that microwave influence was insignificant in the dose, power and time ranges used. The radiation target analysis of the enzymatic decrease due to electron irradiation indicated a very large aggregation of the enzyme molecules. Our data suggest that radiation target analysis is not suitable to measure the molecular mass of lactate dehydrogenase, when frozen enzyme suspensions are irradiated. The D2O-protected enzyme, when exposed to electron irradiation, showed an even larger aggregation according to radiation target analysis, while the microwave irradiation of the protected enzyme led to a similar, though lesser, non-linear behaviour of the frozen enzyme molecules.     

Microwave-Assisted Synthesis and Characterization of Polyurethanes from TDI and Starch

In this work, a microwave-assisted method was developed to prepare polyurethanes from starch or maltodextrin and tolylene-2,4-diisocyanate (TDI). As compared to conventional heating, this new synthetic procedure saves energy, significantly reduces reaction time, and yet entails product yields that are comparable to those of the conventional heating procedure. The reaction products were characterized with NMR, FT-IR, thermogravimetric analysis, and scanning electron microscopy. From these analyses, the polyurethanes made with the conventional and microwave methods are shown to be similar in chemical structure and physical morphology. Furthermore, the ¹H and ¹³C NMR spectra of the starch polyurethanes have been fully assigned for the first time.     

Spectroscopic monitoring for the formation of mesoporous MCM-41 materials upon microwave irradiation

The mesoporous MCM-41 materials were prepared in very short crystallization time (∼40 min) upon microwave irradiation in comparison with conventional hydrothermal heating method. With both microwave irradiation and hydrothermal heating, the MCM-41 formation via supramolecular templating method has been monitored by fluorescence and electron spin resonance (ESR) spectroscopy. Pyrene as a fluorescence probe and 4-(N,N-dimethyl-N-hexadecyl)ammonium-2,2,6,6-tetramethyl piperidinyloxy iodide (CAT16) as a spin probe were respectively dissolved into the micelle solutions to form the MCM-41 precursor gels. These probes allow the monitoring of the supramolecular interaction between the anionic silicate species and the cationic surfactant molecules during the MCM-41 formation. Analyses of fluorescence and ESR spectra indicate that the fast increase of hydrophobicity and microviscosity at the solubilzation sites of the probes results from the accelerated condensation of silicates onto the micelle surface upon microwave irradiation. The fluorescence change from the silicate L-center in the MCM-41 precursor gel also probes the fast silicate condensation upon microwave irradiation. It seems that the fast formation of MCM-41 upon microwave irradiation is ascribed to the microwave-susceptible head groups of surfactant molecules in addition to fast dissolution of the precursor gel.     

Solution Properties of Mixed Starch/Chitosan Revealed by Resonance Light Scattering

The association behavior of starch and chitosan and the dilute solution properties of the starch/chitosan complex were investigated by means of resonance light scattering(RLS) spectra. The interaction between starch and chiotsan was proved by RLS. Based on the results, the appropriate association condition was selected. However, the solution property of starch/chitosan was affected greatly by external factors such as pH value and metal ionic strength. The change of pH, which causes the irreversible transition of solution from transparent into murky, provides some important information of partitioning behavior of the complex in solution. The durative enhancement of RLS intensity for the complex exhibited two inflexions and a plateau in the presence of a certain amount of Fe³⁺. It indicates that Fe³⁺ not only increases the RLS intensity, but also induces the micell-aggregate transition of the complex in solution. Moreover, the thermodynamic parameters for micell formation process at different temperatures, based on the RLS values, were calculated.