蜜胺修饰的偶氮类凝胶因子的合成及其凝胶行为

设计合成了2个双蜜胺修饰的偶氮苯类小分子有机凝胶因子M-AZO-1和MAZO-2.M-AZO-1和M-AZO-2能在多种有机溶剂中形成稳定的凝胶.通过SEM观察凝胶聚集体结构发现,凝胶因子在不同溶剂中形成凝胶的微观形貌结构不同,在乙酸乙酯等极性溶剂中凝胶纤维直径较大,在甲苯和甲基环己烷等非极性溶剂中凝胶纤维直径较小.进一步研究了UV光照对凝胶行为的影响.M-AZO-1和M-AZO-2经365nm UV光照后仍可以形成凝胶,其凝胶聚集体结构变化不明显.     

室温下水凝胶合成的新型方法及测试研究

旨在报道一种新型的水凝胶因子,可在室温下形成凝胶。通过向安替比林-环己烷羰基酯(物质1)的乙醇溶液中加入定量的水可原位、即刻形成凝胶,利用有机合成方法得到了含有吡唑啉酮和环己胺基团的凝胶因子,通过IR,XRD,SEM,TEM等手段对凝胶进行了表征。研究发现,在水含量较低时,凝胶因子分子聚集成为囊泡形状;随着含水量的增大,它的聚集体能实现由0D囊泡向不规整的2D片状结构的转变,并胶凝溶剂。     

Improved photostability of Vitamin A palmitate originating from self-assembled supramolecular gels

Retinyl palmitate(RP) is a derivative of Vitamin A and widely applied as the active component in the fields of cosmetic and pharmaceutics.RP can easily lose its physiological activity under UV irradiation due to its photosensitivity.In this work,it was found that the activity of RP remained 75% after 80 min of UVA irradiation when RP was entrapped in supramolecular gels formed by self-assembly of sorbitol-based gelators.By contrast,the activity of RP in conventional hydroxyethyl cellulose gels only remained 10% under the same conditions.These results showed that the supramolecular gels exhibited a significant protective effect on the photostability of RP.UV spectra of RP in supramolecular gels and corresponding solutions showed no distinct differences,indicating no change of the physicochemical properties of RP.The images of field-emission scanning electron microscopy and fluorescent optical microscopy suggested that the protection by supramolecular gels on the photostability of RP may be attributed to the three-dimensional network structure formed by the self-assembly of the gelators,which reduced the molecular collisions and the degradation process of the photoactivated RP.The present results showed that this protection can be influenced by the structures and the concentration of gelators as well as by the solvent composition.     

Gelation of particles with short-range attraction

Nanoscale or colloidal particles are important in many realms of science and technology. They can dramatically change the properties of materials, imparting solid-like behaviour to a wide variety of complex fluids. This behaviour arises when particles aggregate to form mesoscopic clusters and networks. The essential component leading to aggregation is an interparticle attraction, which can be generated by many physical and chemical mechanisms. In the limit of irreversible aggregation, infinitely strong interparticle bonds lead to diffusion-limited cluster aggregation (DLCA). This is understood as a purely kinetic phenomenon that can form solid-like gels at arbitrarily low particle volume fraction. Far more important technologically are systems with weaker attractions, where gel formation requires higher volume fractions. Numerous scenarios for gelation have been proposed, including DLCA, kinetic or dynamic arrest, phase separation, percolation and jamming. No consensus has emerged and, despite its ubiquity and significance, gelation is far from understood-even the location of the gelation phase boundary is not agreed on. Here we report experiments showing that gelation of spherical particles with isotropic, short-range attractions is initiated by spinodal decomposition; this thermodynamic instability triggers the formation of density fluctuations, leading to spanning clusters that dynamically arrest to create a gel. This simple picture of gelation does not depend on microscopic system-specific details, and should thus apply broadly to any particle system with short-range attractions. Our results suggest that gelation-often considered a purely kinetic phenomenon-is in fact a direct consequence of equilibrium liquid-gas phase separation. Without exception, we observe gelation in all of our samples predicted by theory and simulation to phase-separate; this suggests that it is phase separation, not percolation, that corresponds to gelation in models for attractive spheres.     

两亲性萘双酰亚胺的合成及其凝胶性能

以没食子酸和萘四酸酐为基本原料,通过三步反应,简单高效地合成了两个新的两亲性萘双酰亚胺类化合物(NDI-1和NDI-2).通过IR、~1H NMR、~(13)C NMR、HRMS对目标分子的结构进行了表征,并详细研究了它们在不同溶剂中的凝胶性能.结果表明:NDI-2是一种多功能凝胶因子,不仅可以在非极性溶剂(苯、甲苯、二甲苯)中,还可以在强极性溶剂(DMSO)以及含水溶剂(30%H_2O-THF)中以较低的临界成胶浓度(CGS,3.3～9.5 g/L)形成稳定凝胶.     

Amidourea-based homoduplex as a super organogelator

The amidourea-based homoduplex was developed as a super organogelator,which could form stable gels in wide-tested solvents.And the reversible gel to solution transition was responsive to heat/cool and acid/base stimuli.The organogels were extensively investigated by 1 H NMR,UV-visible absorption spectroscopy,fluorescence spectroscopy,scanning electron microscopy,transmission electron microscopy and powder X-ray diffraction.Based on these data,the gelation mechanism was rationally proposed.The hydrogen-bonded homoduplexes served as the basic assembling units,and further aggregated into three dimensional networks via-stacking and van der Waals interactions,which consequently led to the entangled fibers for the gel formation.     

低分子量凝胶的研究进展及展望

低分子量凝胶是一种超分子体系,具有许多高分子量凝胶不具备的优异性能,如智能性、可降解性、生物相容性等。在生物组织工程、药物缓释及传输、环境保护、传感器制备等方面均有广泛的应用前景。综述了近年来低分子量凝胶的研究进展,介绍了低分子量凝胶的形成机理、分类以及目前的应用状况,并展望了其未来的发展前景。     

干燥控制化学添加剂在制备硅气凝胶中的应用

以硅溶胶为主要原料,通过硅溶胶体系的凝胶过程中添加干燥控制化学添加剂(DCCA),并结合非超临界干燥技术制备了硅气凝胶,研究了DCCA对凝胶过程和最终所得气凝胶品质的影响。DCCA能使凝胶的生成时间增加,凝胶结构均匀化,构成凝胶的基本微粒的粒径有所减小。在一定的DCCA添加量范围内,随着DCCA添加量的增加,所得气凝胶样品的密度有所减小,比表面积增加,微观结构变得更加完善,孔分布也更加集中。不同DCCA对气凝胶品质的影响规律不尽相同,气凝胶的品质就有可能通过调节添加DCCA的种类和量得到控制。     

剪切与吸附对弱凝胶深部调驱作用的影响

分别用玻璃微珠、石英砂、露头砂制作填砂模型，研究了弱凝胶体系的动态性能变化以及剪切与吸附对其深部调驱作用的影响。研究结果表明，动态条件下弱凝胶体系在3种介质中均可发生交联反应，其封堵能力、有效作用距离、深部调驱作用在玻璃模型、石英模型、露头模型中依次降低，水驱后弱凝胶均呈颗粒状。剪切作用可破坏弱凝胶三维结构及聚合物分子链，延长动态成胶时间，降低弱凝胶的封堵强度及其深部调驱作用；吸附作用可富集交联剂，加快交联速度，缩短动态成胶时间，降低弱凝胶本身强度、可运移性及其深部调驱作用。     

乙醇-水溶液中十六烷基三甲基溴化铵的自组装特性

为了研究乙醇-水混合溶液中表面活性剂的自组装特性对多孔无机材料模板法合成的作用,采用稳态荧光法测定了乙醇-水混合溶剂的组成变化对十六烷基三甲基溴化铵(CTAB)临界胶束浓度的影响．结果表明,随着乙醇含量的增加,临界胶束浓度值增大;CTAB在水中的临界胶束浓度值为0．000 9 mol／L,而在乙醇中为0．24 mol／L．进而利用耗散颗粒动力学模拟研究了CTAB在水及乙醇-水混合溶剂中聚集形态的转变过程,并利用分子动力学方法计算了CTAB尾基与溶剂分子间的相互作用能,结果表明,CTAB的疏水尾基与乙醇分子之间的相互作用强,因而CTAB在乙醇中不易形成胶束,这与测定的实验数据的规律性一致．     

Photoresponsive organogel and organized nanostructures of cholesterol imide derivatives with azobenzene substituent groups

Two new cholesterol imide derivatives with azobenzene substituent groups have been synthesized.The compounds possess headgroups of hydrogen or methyl units,respectively.The gelation test revealed that ...     

水-DMF-NaCl系统活度系数和粘度测定

利用电池电动势法测定了298.15K下NaCl在不同DMF含量的水－DMF混合溶剂中的活度系数。结果表明,随着混合溶剂中DMF含量的增加NaCl的活度系数减小,测定了水－DMF－NaCl混合物在不同温度下的粘度。     

Design and optimization of a linker for fusion protein construction

Bivalent, bispecific single-chain antibody fusion protein construction appears to be a promising tool for tumor therapy. One of its drawbacks is that the function and activity of the fusion proteins have varied affinity and/or anti-tumor activity compared with the original molecules from which they are derived. A more optimized linker for fusion proteins would confer more favorable biological activities upon bispecific single-chain antibodies. Thus, it is critical to design and optimize an inter-peptide linker. With different functional domains and optimized linkers, fusion proteins provide a solid base for targeted immune therapy for malignancies. In this paper, we review the inter-peptide linker studies and the design of an optimized linker using genetic algorithms. The spatial structure of the fusion protein can be predicted by using genetic and bioinformatics research. Based on current research, the future focus will be on different correlation models to perform simulations of spatial structures and drug molecule design.     

溶剂类型对GAP凝胶性能的影响

采用溶胶-凝胶法分别在5种溶剂中制备出了GAP凝胶,利用红外光谱、TG、DSC对其结构及热性能进行分析,并测试了其交联密度相对特征值及凝胶质量分数.结果表明,所制备的GAP凝胶均具有良好的热稳定性,密度为0.455～0.556g/cm3,且随着所选用的溶剂的极性减小,GAP凝胶的质量分数与交联密度增大,耐热性提高,分解放热增大,机械性能增强.     

单L-苯丙氨酸衍生物对乙醇/水混合溶剂的凝胶化研究

考察了单L-苯丙氨酸衍生物——L-3-[(3-硬脂胺酰基)-3-苯基-丙酰基]丁酸(SPAB)在乙醇/水混合溶剂中的凝胶行为,结果表明SPAB在乙醇/水的体积比从9:1到2:3的乙醇/水混合溶剂中能形成稳定的、热可逆的超分子凝胶。而在乙醇/水(V/V=1)溶液中的最低凝胶化浓度(MGC)低至1.2 mg/m L。凝胶的相转变温度(TGS)随凝胶因子浓度增加而升高。扫描电镜(SEM)观察到SPAB在乙醇/水混合溶剂中形成了相互交联的带状纤维聚集体。红外光谱(FTIR)结果表明SPAB分子中酰胺基团间的氢键、烷基的疏水作用以及水与SPAB分子中的羧基间的氢键是分子自组装的主要驱动力。     

凝胶注模的凝胶反应动力学和均匀性

研究凝胶注模反应动力学与反应条件对凝胶均匀性的影响,获得合理的凝胶反应条件.研究结果表明:增加引发剂浓度、催化剂浓度和单体浓度或者升高起始反应温度,凝胶反应诱导期和反应期均缩短,但单体/交联剂比例对诱导期和反应期影响不大；增加悬浮液的固相体积分数,诱导期缩短而反应期却延长；引发剂浓度、催化剂浓度和单体浓度过高或过低,均会降低凝胶均匀性.凝胶注模单体浓度较合适质量分数的范围为10％～20％,起始反应温度应控制在20～40℃；随着单体与交联剂质量比的降低,凝胶均匀性下降:当单体与交联剂质量比低于某一值时,凝胶均匀性急剧下降.单体与交联剂的质量比应高于20∶1.     

非共价相互作用对中心手性的影响及中心手性的定义

建立在van't Hoff碳正四面体构型学说基础上的中心手性的概念未涉及非共价相互作用对分子中心手性的影响.可以想像,当某原子连有两个相同的原子或基团(如氢原子)时,可因非共价相互作用(如分子内氢键)的存在(如只与其中的一个氢原子形成氢键)成为不等性原子或基团.考虑到非共价相互作用对分子中心手性可能产生的影响,中心手性的概念似应为:一个原子(如C,N)的四支键分别指向四面体的各顶点,并分别键连四个不等性原子或基团(包括孤电子对)时,则该原子是手性的.     

离子选择电极在混合溶剂中的应用Ⅱ．Cu（Ⅱ）与甘氨酸配合物在醇＋水溶剂中的稳定常数

本文利用离子选择电极法测定了２５℃，Ⅰ＝０．１时，钢（Ⅱ）－甘氨酸配合物在纯水及８．０％，１６．３％，２５．０％，３４．２％，４３．８％叔丁醇或异丙醇＋水混合溶剂中的一级稳定常数，计算了配位反应的自由能变化及该配位反应从纯水到上述各混合溶剂的转移自由能。实验结果表明：随着混合溶剂中有机组分的加入，配合物更趋于稳定．     

鱼明胶/海藻酸钠复合凝胶特性研究

为改善鱼明胶单网络凝胶的性能,利用复凝聚法制备不同质量浓度的鱼明胶/海藻酸钠复合凝胶,研究其表观特征、色度值和流变性质,并以单一鱼明胶凝胶为对照。实验结果表明,随着鱼明胶质量浓度提高(0.06~0.10g/mL),单一凝胶弹性增加,网络结构更加优良,但在较低质量浓度(0.06、0.07g/mL)时,凝胶脆性大、易破碎；复合凝胶整体展现了良好的凝胶特性,成型效果较好,且随着海藻酸钠质量浓度的提高(0.01~0.03g/mL),凝胶强度持续提高。由此表明,海藻酸钠的加入可以改善复合凝胶的凝胶强度。通过研究不同质量浓度鱼明胶与海藻酸钠在不同阶段的凝胶性质,为二者复合物的实际应用提供了更多理论依据。     

硫化氢对冻胶型堵剂的影响

研究了H2S对常规冻胶型堵剂成冻时间和冻胶强度的影响,这些冻胶型堵剂包括交联聚丙烯酰胺形成的铬冻胶和酚醛树脂冻胶.探讨了H2S对冻胶型堵剂影响的作用机理.结果表明:H2S对无机铬交联体系的影响较大,而对有机铬交联体系和酚醛树脂交联体系的影响相对较小;对于无机铬交联体系,H2S能迅速将Cr6+还原为Cr3+,提高交联HPAM的速度,而当H2S含量偏高时,被还原出的Cr3+会与过量的H2S生成Cr2S3沉淀,不能形成整体冻胶;对有机铬和酚醛树脂交联体系的影响主要体现在pH值的变化上.当选择冻胶型堵剂应用于含H2S的油气藏时,最好选用酚醛树脂冻胶.