高取代度阳离子高直链淀粉的制备及絮凝性能

以高直链玉米淀粉为原料,NaOH为催化剂,2,3-环氧丙基三甲基氯化铵(ETA)为阳离子醚化剂,成功的制备了高取代度阳离子高直链淀粉。分别研究了反应溶剂、反应温度和时间、醚化剂用量、催化剂浓度等因素对产物取代度的影响。实验结果表明,当n(NaOH)/n(ETA)/n(脱水葡萄糖单元AGU)=0.30,反应溶剂为二氧六环和水(V/V=1∶1),n(ETA)/n(AGU)=2,反应温度为60℃,反应时间7h时,制备的阳离子淀粉取代度(DS)可达到1.27。采用FTIR、1 H-NMR和SEM表征了高取代度阳离子高直链淀粉的结构。絮凝实验表明,阳离子高直链淀粉可以作为一种良好的新型絮凝材料。     

高取代度阳离子淀粉的制备

以玉米淀粉及 3 氯 2 羟丙基三甲基氯化铵 (CHPTMA)为原料 ,运用改进常温干法—预干燥干法制备了高取代度季铵型阳离子淀粉。考察了水的质量分数、氢氧化钠用量醚化剂用量、反应温度和反应时间对取代度和反应效率的影响 ,确定了反应配方和反应条件 ,并对产物进行了性能测定。结果表明 ,产物具有良好的分散性和溶解性 ,具有一定的工业应用价值。     

阳离子淀粉/质粒DNA纳米传递系统的制备及特性

利用阳离子淀粉制备了阳离子淀粉/质粒DNA纳米传递系统,通过凝胶电泳、激光粒度分析和原子力显微技术研究了不同取代度和N/P(氮/磷)摩尔比对传递系统复合性能和形貌特征的影响;进一步研究了DNase I内切酶消化液、模拟体液和溶菌酶溶液等不同模拟体内环境对阳离子淀粉/质粒DNA传递系统稳定性的影响规律,并考察了阳离子淀粉与质粒DNA复合性能随细胞内涵体pH变化的规律。结果显示,较高N/P比和阳离子取代度下的阳离子淀粉/质粒DNA传递系统复合性更好,抗DNase I和抗溶菌酶能力更强,且质粒DNA传递系统能够抵御pH=1.2的酸性环境,而在pH=4.0和pH=7.4的环境下N/P摩尔比>5时,能保护质粒DNA使其不被酸性环境破坏。     

溶剂法制备高取代度马铃薯羧甲基淀粉的研究

以马铃薯淀粉为原料,乙醇为溶剂,用溶剂法制备高取代度羧甲基淀粉。应用正交设计法研究了影响淀粉羧甲基化反应的各种因素,确定了制取高取代度(DS>1.3)羧甲基淀粉制的反应条件是:醚化温度50℃,醚化时间120min,原料最佳摩尔比:n(淀粉):n(氯乙酸)=1:3,n(氢氧化钠):n(氯乙酸)=2.5:1。     

醋酸酯淀粉抗菌材料的性质

以疏水性的醋酸酯淀粉为基材,壳聚糖为抗菌剂制备了醋酸酯淀粉抗菌材料。通过考察醋酸酯淀粉取代度对壳聚糖分散性、材料力学性质、热性质和抗菌活性的影响,发现醋酸酯淀粉的取代度由1.9增加到2.9,抗菌材料表面和断面越均一,壳聚糖的分散性越好;但高取代度会削弱淀粉分子与壳聚糖分子间的相互作用力,使抗菌材料的断裂伸长率由33.7%降低至8.9%,玻璃化转变温度由74.8℃升高至86.4℃,拉伸模量由205 MPa增至260 MPa。同时过高的取代度又会影响壳聚糖的溶出,降低材料的抗菌活性。     

离子液体中无催化剂法合成淀粉醋酸酯的结构与性能

以离子液体(ILs)氯化1-丁基-3-甲基咪唑(BMIMCL)为反应介质,无催化剂均相合成了高取代度的高直链玉米淀粉醋酸酯,利用红外光谱(FT-IR)、核磁共振(1H-NMR)、X射线衍射(XRD)和热重分析(TGA)对不同取代度(DS)的淀粉醋酸酯进行表征。结果表明,在BMIMCL中,无催化剂条件下,高直链玉米淀粉可与醋酸酐发生较好的均相反应,所合成的淀粉醋酸酯不存在淀粉原有的颗粒结构和结晶结构。并且,随着取代度的增加,XRD曲线中9°处的弥散峰增强,其热稳定性逐步提高。     

取代基团在变性淀粉颗粒中的分布

详细论述了取代基团在变性淀粉颗粒表面和内部、结晶区和无定形区、支链和直链上分布的研究原理和方法,认为变性基团可能优先分布在颗粒的无定形区域,但当反应条件十分苛刻时也能进入颗粒的结晶区域;变性优先发生在颗粒的表面,也会在颗粒的内部发生,表面的取代度是整个淀粉颗粒平均取代度的3~4倍;变性既可以发生在直链淀粉又可以发生在支链淀粉的非还原端和分支点周围,并且直链淀粉的取代程度比支链淀粉要高。     

阳离子掺杂措施优化铜锌锡硫硒电池性能的研究进展

铜锌锡硫硒(Cu₂ZnSn(S,Se)₄,简称CZTSSe)薄膜太阳能电池因其组成元素地壳含量丰富，低毒环保等优点被科学家们认为是适合未来大面积发展的一类太阳能电池。当前，该类太阳能电池的效率一直受到吸收层中高的阳离子无序度和器件的低开路电压的限制。为此，科学家们提出“阳离子掺杂措施”,即：通过引入其他阳离子，减少本身的阳离子无序度，从而提高电池器件的光电转换效率。事实也证明，阳离子掺杂措施在提升电池器件性能方面有着重大的意义。基于此，详细阐述了阳离子掺杂措施在优化铜锌锡硫硒电池器件性能方面的研究进展，包括：阳离子(如：钠、钾、锑)的额外添加和阳离子取代(如：锂/银取代铜、锰/镁/钡/镉取代锌、锗取代锡)措施，并得出结论：最有前景的阳离子是镉和锗离子，考虑到镉的有毒性，所以锗应该是优化CZTSSe电池性能方面最有应用前景的一种元素。     

淀粉疏水改性及其应用

传统变性淀粉只有单一的亲水性质,淀粉的疏水改性成为该领域的研究热点之一,介绍了国内外淀粉疏水改性的研究现状及存在的问题,认为淀粉疏水改性要重点解决低成本、环境友好制备高取代度的产物.     

醋酸酯淀粉的制备与初步表征

以淀粉为基料,以冰醋酸和醋酸酐为乙酰化试剂,以硫酸为催化剂,制备了醋酸酯淀粉;用红外光谱仪对醋酸酯淀粉进行了初步表征,并用酸碱滴定法测试了其取代度和乙酰基含量;系统讨论了反应温度和反应时间等对醋酸酯淀粉的取代度、乙酰基含量的影响.实验结果表明:随反应温度升高和反应时间延长,乙酰基含量和取代度增大;当反应温度为50℃,反应时间为6h,催化剂质量浓度为0.1%时,取代度和乙酰基含量较高.     

Evaluation of the emulsifying properties of some cationic starches

Different cationic potato, maize, and waxy maize starches were evaluated for their emulsifying properties. Emulsions were prepared using 20% (w/w) arachidic oil and 80% (w/w) water. Emulsions with the cationic starches as emulsifier in a concentration ranging from 1% to 5% (w/w) were prepared and characterized by droplet size and viscosity measurements, and the stability was evaluated visually and by electrical conductance measurements. None of the cationic potato, waxy maize starches, and maize starches with a low degree of substitution (DS) showed adequate emulsifying properties. Emulsions prepared using non-pregelatinized (C ☆ bond 05914, 2% and 5% w/w; C ☆ bond 05907, 5% w/w) and pregelatinized (C ☆ bond 12504, 5% w/w) cationic maize starches with high-DS were visually stable. The initial mean droplet volume diameter of the emulsions prepared with these cationic starches in a 5% (w/w) concentration was similar and ranged from 2.40 to 2.84 μm however, there was an important difference in droplet size distribution. The droplet size distribution of the emulsions prepared using the non-pregelatinized high-DS cationic starches was markedly narrower than in the case of the emulsions prepared using the pregelatinized high-DS cationic starches. The droplet size of the emulsions remained almost constant during 120 days of storage. Visual inspection and electrical conductance measurements showed that these emulsions were stable for at least 120 days.     

MAH对干法酯化淀粉/PLA复合材料性能的影响

以玉米淀粉和马来酸酐(MAH)为原料,通过干法合成MAH酯化淀粉,通过熔融挤出法制备酯化淀粉/聚乳酸(PLA)复合材料.研究了MAH用量对复合材料结晶度和相容性的影响,同时考察了相容性和结晶度的变化对复合材料热性能、熔融流动性能、力学性能、耐水性能和流变性能的影响.FTIR结果证明通过干法成功合成了MAH酯化淀粉.酯化淀粉的取代度随MAH用量增多逐渐增大,反应效率高达90%.XRD和DSC结果表明:随着MAH用量增多,酯化淀粉/PLA复合材料的结晶度逐渐降低,淀粉和PLA的相容性逐渐提高.结晶度的降低和相容性的提高使复合材料的玻璃化转变温度逐渐降低,熔融流动性提高,耐水性提高.在力学性能和流变性能受相容性和结晶度的共同影响下,酯化淀粉中MAH用量从0增加到1.0wt%时,复合材料拉伸强度、弯曲强度、储能模量和复数黏度都逐渐增大,MAH用量超过1.0wt%后,性能逐渐降低.     

Acetylation enhances the tabletting properties of starch

The aim of this study was the evaluation of starch acetate (SA) powders used as tablet excipients. Deformation during powder volume reduction, strain-rate sensitivity, intrinsic elasticity of the materials, and tensile strength of the tablets were examined. Results showed that SA with the lowest degree of substitution (ds) still possessed characteristics of native starch granules. Due to dissolution in synthesis, the properties of higher ds SAs depended on precipitation and drying processes. The acetate moiety, perhaps in combination with existing hydroxyl groups, was a very effective bond-forming substituent. The formation of strong molecular bonds increased, leading to a very firm and intact tablet structure. Small changes existed in compression-induced deformation due to acetylation. Some fragmentation was induced due to the slightly harder and more irregular shape of high-substituted SA particles. The plastic flow under compression was enhanced. Acetylated material was slightly less sensitive to fast elastic recovery in-die, but somewhat more elastic out-of-die. In spite of their superior bonding, SAs under compression behaved similarly to native starches. It was concluded that deformation properties were more the consequence of the molecular chain structure properties of the starch polymer than the effect of the acetate moiety itself. In contrast, the opposite seemed to be the case with the extensive improvement in bond-forming properties.     

Effect of starch type on miscibility in poly(ethylene oxide) (PEO)/starch blends and cytotoxicity assays

This study reports results on the miscibility of polymer blends based on PEO and different starches (unmodified, cationic, and hydrophobic) and their respective cytotoxicity. Films of PEO/starch blends at different weight ratios (95/05, 90/10, 80/20, 70/30, 65/35, and 60/40), as well as films of pure PEO as control, were prepared by casting methodology. Several techniques, such as SEM, WAXS, FTIR, and FT-Raman spectroscopy were used in this study for evaluating blend miscibility. The results revealed that the miscibility of such blends is dependent on the type of starch used. Regarding the PEO/unmodified starch blends, it was concluded that the system is miscible in the ratio range from 90/10 to 65/35. Although the PEO/hydrophobic starch blends are miscible in all the studied range, blends of PEO and cationic starch are immiscible, regardless the blend ratio. The different samples presented distinct cytotoxic behaviors. PEO and hydrophobic starch presented no relevant toxicity (CC_50/72 > 2.5 mg/mL). Otherwise, the cationic starch was the most harmful for the cells. The blends presented cytotoxicity values between those of PEO and cationic starch.     

高流动性、强疏水性淀粉的制备及性能

采用干法改性处理技术对玉米淀粉进行改性处理,制备得到具有高流动性及强疏水性的玉米淀粉。通过活化指数、接触角、流动时间及休止角等指标,对改性前后玉米淀粉的流动性及疏水性进行评价。结果表明,经过改性处理,玉米淀粉由亲水性表面转变为强疏水性表面,并且改性后的玉米淀粉具有了良好的流动性。X射线衍射(XRD)测试结果表明,改性处理并没有改变玉米淀粉的结晶结构,只是改变玉米淀粉的表面性质。     

Crosslinked Starch as Sustained Release Agent

Different types of crosslinked starches and pregelatinized-crosslinked starches were evaluated for their use as hydrophilic matrices. Some fundamental properties of these chemically modified starches, e.g. granule swelling power and viscosity of the dispersion in function of pH and ionic strength, were studied. Dissolution tests and the rate and amount of water uptake were evaluated on tablets containing theophylline and modified starch (40/60 w/w), compressed on an instrumented tablet press at three different pressures (50,200 and 300 MPa.). Theophylline releasing profiles were determined using the paddle system at a rotational speed of 50 rpm Water, simulated gastric fluid, and simulated intestinal fluid were used as dissolution media. Crosslinked starches showed a poor swelling power and dispersion viscosity in comparison to pregelatinized starch and pregelatinized-crosslinked starches. The pregelatinized-crosslinked starches developed less swelling power than the pregelatinized starch, but they showed higher dispersion viscosity than the pregelatinized starch. The viscosity of all starch dispersions was not affected by ionic strength. An alkaline pH dramatically increased the dispersion viscosity of pregelatinized starch and pregelatinized-crosslinked starches. Drug dissolution rate was lower for tablets containing pregelatinized starch than for tablets containing pregelatinized-crosslinked starches. This phenomenon can be related to the rate and amount of water uptake. The dissolution rate seemed not to be influenced by the compression force nor by the composition of the dissolution media. The results indicate that crosslinked starches, either pregelatinized or not, are not suitable as sustained release agents.     

淀粉/PVA囊化含羧基类除草剂的缓释性能

以2，4-二氯苯氧乙酸(2，4-D)和2，4，5-三氯苯氧乙酸(2，4，5-T)作为模型药物，通过测定囊药体系的水溶胀程度、栽药量、囊化效率和释放速率，研究了淀粉／PVA囊材对含羧基类除草剂的缓释特性，探讨了淀粉品种、PVA含量、PVA分子量、PVA醇解度和栽药量对该除草荆缓释性能的影响。实验结果表明。淀粉／PVA囊材的缓释性能明显优于原淀粉囊材。     

超声波处理对蜡质玉米淀粉糊流变性质的影响

研究了超声波处理前后蜡质玉米淀粉的流变性质变化。采用超声波对含水量70%的蜡质玉米淀粉进行处理,运用旋转黏度计对处理前后的淀粉糊特性进行研究。结果表明,不同超声功率处理的蜡质玉米淀粉糊均为假塑性流体;超声处理的蜡质玉米淀粉糊表观黏度随剪切速率的升高而降低,随着体系浓度增高,剪切稀化增强;超声处理的淀粉糊其触变性随超声功率的增大而减小。     

Enzyme-aided investigation of the substituent distribution in cationic potato amylopectin starch

The distribution of substituents along the polymer chain in cationic potato amylopectin starch, modified in solution, granular slurry, or dry state, was investigated. The starch derivatives were successively hydrolyzed by different enzymes, followed by characterization of the hydrolysis products obtained by means of electrospray mass spectrometry (ESI-MS) and matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). ESI-MS and MALDI-MS were proved to be appropriate techniques for identification of the substituted hydrolysis products, for which there are no standard compounds available. No highly substituted oligomers were found in the hydrolysates, which was taken as an indication of a more or less homogeneous distribution of cationic groups in the amylopectin molecules. Furthermore, from the results obtained it was suggested that the enzymes cleave glucosidic linkages only between unsubstituted glucose units and, preferentially, linkages in sequences containing more than two adjacent unsubstituted units. The determination of the amount of unsubstituted glucose produced from every successive hydrolysis step revealed slight differences between the different starch samples with respect to the homogeneity of the substitution pattern. Among the three samples under investigation, starch cationized in solution was found to have the most and dry-cationized starch the least homogeneous distribution of substituents.