新型偶氮苯基团凝胶因子的合成及其光响应行为

设计合成了两种新型偶氮苯类凝胶因子Azo-1和Azo-2，两者均能在多种有机溶剂中形成稳定凝胶. 利用扫描电子显微镜观察凝胶的显微结构，发现随着溶剂极性增大，凝 胶纤维束直径有所增大. 采用Hansen溶度参数对凝胶性能进行分析，形成凝胶的溶剂集中 分布在Hansen空间的一定区域，凝胶的Tgel主要受色散参数的影响. 通过紫外-可见吸收光谱考察了凝胶因子在稀溶液及凝胶状态的光谱性质，在溶液中Azo-1的偶氮苯基团的光致 反-顺异构转变速度远快于Azo-2，仅Azo-1在四氢呋喃和三氯乙烯等溶剂中表现出光致凝胶-溶胶的转变. 光照前后的凝胶微观形貌结构发生显著的改变. 通过Hansen溶度参数分析发现，能够发生光致相转变的溶剂在Hansen空间基本处在同一直线上.     

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.     

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。     

一种L-苯丙氨酸衍生物的合成及其凝胶化研究

本研究设计合成了一种可自组装的L-苯丙氨酸衍生物凝胶因子-3-{[2-(十二酰胺基)-3-苯丙基] 酰氨基}丁酸 (1),并用1H-NMR、元素分析和FTIR等手段对其结构进行了表征.考察了其在27种常见溶剂中的凝胶行为,结果 表明化合物1可使其中的11种溶剂凝胶化而形成热可逆的超分子凝胶.室温下1在苯中的最低凝胶浓度为0.2%,苯凝胶的凝胶-溶胶相转变温度(Tgel)随凝胶因子的浓度的增加而升高.     

一种新型苝衍生物的凝胶行为

采用离子自组装方法,以苝酐的羧酸盐及阳离子表面活性剂二甲基二十八烷基溴化铵(DOAB)为原料,室温下合成一种新型苝衍生物.借用核磁共振仪(NMR)和傅里叶变换红外光谱仪(FTIR)确定目标产物的化学组成和结构.利用透射电镜(TEM)、X射线衍射仪(XRD)、小角X射线散射仪(SAXS)等表征衍生物的凝胶聚集体形貌及排列结构.结果表明:这种苝衍生物能够在芳香环间的π–π相互作用下,通过自组装过程形成有序排列的聚集体,其在甲苯中的凝胶呈现典型的层状结构,苝环之间的π–π相互作用是其形成凝胶的主要驱动力,相互缠结的烷基链与溶剂之间范德华力促使凝胶结构更加稳定.     

溶胶-凝胶法制备多晶氧化铝纤维的研究

以铝粉和六水氯化铝为主要原料、水为溶剂,采用溶胶-凝胶法制备了稳定的多晶氧化铝纤维.结合IR,TG-DTA,XRD等研究手段推测凝胶纤维的化学结构和凝胶的烧结过程,以SEM对凝胶纤维热处理后的显微形貌进行观察.研究表明溶胶在1 200℃热处理后可得到α-Al2O3多晶纤维,且微量氯化镁随铝粉同时加入AlCl3 * 6H2O水溶液中能显著改善纤维的显微形貌,减少裂纹的产生;而直接将氯化镁加到溶胶中则无法得到光洁的纤维形貌.     

高压匀质处理对纳米纤维素自聚集特性及气凝胶结构的影响

木材细胞壁的重要组成部分是许多直径在纳米尺度、具有高长径比、高比表面积和丰富表面基团的纤维素分子聚集体。基于"自下而上"的思想,利用层层分离法从木粉中分离出纳米尺度的基元纤丝。首先,通过化学和超声预处理并结合高压匀质处理的方法从木材中分离制备出纳米纤维素(CNF);然后,通过冷冻干燥的方法将CNF进一步组装加工成纳米纤维素气凝胶。研究发现,超声结合匀质的方法,可得到均匀纤丝化的CNF,具有低直径尺寸分布(纤丝直径为1~3 nm)和高长径比特征,但氢键作用的影响使得单根纤丝又易重构为簇、带状的聚集体形式。随着CNF溶液浓度的增大,所形成的气凝胶密度增大,孔隙度降低,结构由以纤维为主,转变为纤丝交织的片层结构。本研究所得的气凝胶可广泛应用于包装、生物医药、吸附材料等领域。     

基于萘酰亚胺的功能凝胶因子的合成及其凝胶性能

以三聚氯氰为原料合成一种含有酰胺结构的三嗪中间体,与1,4,5,8-萘四甲酸二酐缩合得到萘酰亚胺衍生物NDI-M,运用1HNMR,13CNMR和红外光谱等手段对NDI-M的化学结构进行确认。采用试管倒转法考察NDI-M的凝胶性能;利用扫描电镜(SEM)观测NDI-M凝胶的微观形貌;通过紫外-可见吸收光谱和荧光光谱等研究NDI-M凝胶的光物理性能。研究结果表明:NDI-M在甲苯、二甲苯、乙酸丁酯和甲基丙烯酸丁酯等有机溶剂中均可形成热可逆的凝胶,除在乙酸丁酯中其临界凝胶浓度(CGC)为30 mmol/L外,在其他溶剂中均为20 mmol/L,且在不同的溶剂中形成的凝胶形貌结构有所差别;与溶液的光谱性质相比,形成凝胶后NDI-M的Stokes位移显著增大,不同凝胶的光谱性质表现出明显差异。     

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。     

水凝胶体系中CuS纳米纤维的模板合成

以N-十二酰-L-丙氨酸在乙醇/水混合溶剂中形成的水凝胶为模板, 用两种方法在水凝胶体系中, 利用离子的原位自组装合成了CuS纳米纤维. 获得的样品用透射电镜、 红外光谱和X射线衍射进行了表征, 不同尺寸的CuS纳米纤维可以通过改变矿化条件获得.     

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.     

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 ...     

Preparation of dicholesteryl-derivatives: The effect of spatial configuration upon gelation

To investigate the effect of spatial configuration on the gelation properties of low molecular mass gelators(LMMGs),four novel di-cholesteryl derivatives have been specially designed and synthesized by introducing the cis-/trans-isomers of butene diacid and the optical isomers of D/L-phenylalanine into the linker between two cholesteryl moieties.These isomers have been denoted as MaDC,FaDC,MaLC and FaLC,respectively.The gelation properties of the compounds were examined in 26 organic solvents,and it was found that the trans-configuration is more favorable for the gelation,but the chirality of the linker shows little effect to the gelation.FaDC has the strongest gelation ability among the four isomers.Interestingly,FaDC and FaLC display phase-selective gelation of benzene,toluene and xylene from their mixtures with water at room temperature,which establishes a foundation for the purification of water contaminated by oil or aromatic solvents.SEM and CD spectroscopy studies revealed that the spatial configuration of the linkers of the gelators affects significantly the aggregation mode,the morphologies and the chirality of the network of the gels.Moreover,the different aggregation behaviors also have an impact on mechanical properties of the gels,which are consistent with the results from rheological studies.Furthermore,temperature-and concentration-dependent 1 H NMR and FTIR measurements demonstrated that intermolecular hydrogen bonding and-stacking are the main driving forces for the formation of the gels.     

PLA纤维的性能研究

本文研究了PLA纤维的表面形态、物理机械性能、吸水性、在碱性洗涤剂中的收缩性,以及酸、碱和有机溶剂对PLA纤维的强力损伤程度.结果表明:PLA纤维的强度与形态和PET纤维相近,吸水率比棉小但比PET纤维大,PLA纤维在碱性条件下缩水率和强力损失速率大,PLA纤维抵抗酸碱和有机溶剂的能力大小为:丙酮＞盐酸＞碳酸钠＞氢氧化钠.     

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。     

Thermal Properties of Crosslinking Modified Ultrahigh Molecular Weight Polyethylene Fibers by Ultra-Violet Irradiation

By means of ultra-violet(UV)irradiation with photoini-tiator and multifunctional crosslinking agent,thecrosslinking modification of ultrahigh molecular weightpolyethylene(UHMWPE)fibers prepared by gel-spin-ning was carried out.Thermal properties of fiber sampleswere examined using differential scanning calorimetry(DSC),thermomechanical analysis(TMA)apparatusand a manual device.The results indicated that the opti-mal irradiation energy is 250-400 mJ/cm~2,heat-andcreep-resistant behaviors of modified fibers have beenimproved.     

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.     

微波辐射下神木-府谷烟煤有机质的溶出规律及组成结构

提高煤中有机质的可溶性,从分子水平上了解煤中可溶有机质的组成结构,是实现煤炭资源高效清洁利用的关键性科学问题.本文在微波辐射下对神木-府谷烟煤(SFBC)进行溶剂萃取,考察了微波辐射功率、辐射时间以及溶剂类型对SFBC萃取过程的影响,并利用气相色谱/质谱联用仪(GC/MS)分析了萃取物的组成.结果表明:微波辐射40min时,SFBC的萃取率随微波功率的提高而降低,微波辐射10、20和30min时,SFBC的萃取率随微波功率的提高呈先增加后减小的趋势;SFBC的萃取率与溶剂的介电常数有关,在介电常数较小的四氢呋喃中萃取率最高(5.6%);萃取物主要由脂肪烃和芳烃组成,推测脂肪烃和小分子的芳烃较易从煤的大分子网络中游离出来.     

Fluoro-Compounds in Electrolytes for Energy Storage Devices

1 Results Electrochemical energy storage devices such as lithium-ion batteries[1-2] and double-layer capacitors[3-4] have attracted a great deal of attention because of their potential application to electric hybrid vehicles. They utilize nonaqueous electrolyte solutions comprising from organic solvents and lithium or quaternary ammonium salts with fluorine-containing anions. This is because the relatively large anions with electron-withdrawing atoms enable ionic dissociation in dipolar aprotic solvents...     

顺丁烯二酸甲基三丁基锡的合成和性能的研究

本文报导顺丁烯二酸甲基三丁基锡的制备方法和合成条件。使用红外光谱、质子核磁共振谱,元素分析和分子量测定法等对该化合物的性能进行了研究。实验结果表明,顺丁烯二酸甲基三丁基锡在固态或在某些有机溶剂(如硝基苯、氯仿等)中均倾向于形成复合物。该化合物能溶于普通有机溶剂。