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.     

4-氨基水杨酸在一种超分子水凝胶中的释放行为研究

一种基于L-苯丙氨酸衍生物的小分子量凝胶因子在水中可以自组装形成超分子水凝胶.利用4-氨基水杨酸(PAS)为模型药物分子,研究了该水凝胶所包覆PAS的释放行为.凝胶因子和PAS分子间存在的强相互作用使包覆PAS水凝胶的相转变温度TGS明显降低.利用分光光度法,分别考察了凝胶因子浓度、温度、PAS浓度以及接受介质的pH对释放速率的影响.结果表明:当凝胶因子浓度增加,PAS释放速率明显降低;提高温度或提高包覆PAS量,都可以提高释放速率;在不同pH的缓冲溶液接受介质中的不同阶段,PAS表现出不同的释放行为,在3.0 h内,PAS分子的累积释放率符合Higuchi方程,属扩散控制的Fickian释放机理.     

N-乙烯基-2-吡咯烷酮辐射聚合的溶剂效应

以水作溶剂,N-乙烯基-2-吡咯烷酮辐射聚合得到了聚N-乙烯基-2-吡咯烷酮水凝胶。以乙醇或丙酮作为溶剂时,前者情况下的聚合速度大于后者。这些现象,可用水、乙醇能与N-乙烯基-2-吡咯烷酮形成氢键来解释。聚合反应终止动力学,不受溶剂性质的影响,都属于双分子终止反应。     

联苯胺的电子吸收光谱及其氢键效应

本文研究联苯胺在不同溶剂和不同浓度时的电子吸收光谱.当溶剂从正庚烷改变为二(口恶)烷,乙醇和乙醚时、联苯胺的电子吸收谱带向红移。在不同溶剂和不同浓度下,这红移的大小不同。观察结果表明:联苯胺和所用的极性溶剂形成分子间氢键。根据实验结果提供了联苯胺和所用极性溶剂分子间形成的各种可能的氢键模型.     

氢氰酸与水的异构化反应密度泛函理论研究

采用电子结构理论中的B3LYP密度泛函方法(DFT),在B3LYP/6-311 G(3df,2pd)水平上,在气相和水相中分别研究了异氰酸与水通过分子间氢键首尾相连,形成五元环过渡态,再转换成氢氰酸的异构化反应.计算结果表明,在水相中异构化过程的活化能比在气相中低,无论在气相还是在水相中异氢氰酸通过水氢键转化成氢氰酸容易些,而氢氰酸由水氢键转化成异氢氰酸相对要困难些,分子间氢键和溶剂化效应在异构化反应过程中起到重要的作用.     

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．     

干燥溶剂介质对常压制备SiO2气凝胶的影响

以正硅酸乙酯和乙醇等为原料,通过溶胶-凝胶、表面修饰及溶剂置换等后续工艺,实现常压干燥法制备块状SiO2气凝胶,并考察干燥溶剂介质对气凝胶常压制备的影响。研究结果表明:采用混合溶剂干燥的SiO2气凝胶性能较单一溶剂更佳,以正己烷和甲苯混合溶剂制备的SiO2气凝胶性能最优,具有低表观密度(0.102 7 g/cm3)、高比表面积(928.4 m2/g)、大孔容(3.295 cm3/g)及疏水性良好等特性。     

物理交联聚乙烯醇凝胶中氢键作用研究

采用反复冷冻-解冻法制备聚乙烯醇(PVA)凝胶.采用Hakee RS300动态应力流变仪,利用动态力学分析方法研究PVA物理交联凝胶的力学性能及氢键作用.结果表明,PVA水凝胶及PVA/DMSO凝胶的剪切模量,物理交联密度及最大抗张强度均随着PVA浓度的增加而增大;同一浓度下,PVA水凝胶的剪切模量及物理交联密度大于PVA/DMSO凝胶,但氢键活化能小于PVA/DMSO凝胶.     

羧基化聚己内酯基有机水凝胶的制备及其在信息存储方面的应用

合成了一种制备过程简单、显示信息方便的有机水凝胶。首先，通过端羟基与异氰酸酯的反应，制备了两端带有碳碳双键的羧基化聚己内酯(PCCL)预聚物；然后，将该预聚物与交联剂N,N’-亚甲基双丙烯酰胺(BIS)混合，通过自由基聚合于乙醇中制备了PCCL基有机凝胶；最后，利用溶剂置换法实现了有机凝胶与有机水凝胶之间的转变，获得了PCCL基有机水凝胶。通过核磁共振氢谱(¹H-NMR)、傅里叶变换红外光谱(FT-IR)以及紫外透过率等测试表征了聚合物和有机水凝胶的组成和结构，探究了有机水凝胶在不同溶剂中的光学性质。结果表明，该有机水凝胶在不同的溶剂中表现出明显的透明度变化，在不良溶剂中发生微相分离，在良溶剂中发生溶胀。PCCL基有机水凝胶的设计策略和溶剂响应性有望用于信息存储与显示平台。     

含电解质溶剂体系ET(30)参数的测定及其在溶剂解反应动力学盐效应研究中的应用

利用作者合成的ET(30)染料,测定了85%(V/V)1,4-二氧六环+水+LiClO4,75%(V/V)1,4-二氧六环+水+LiClO4,80%(V/V)乙醇+水+LiClO4,乙醇+Et4NCl溶液的ET(30)值,考察了ET(30)值与一些溶剂解化学反应动力学数据间的关系.结果表明:一些溶剂解反应的速率常数与溶剂的ET(30)值有线性关系.本文从反应机理和溶液中的优先溶剂化作用的角度对这种现象进行了解释和说明.     

氢键诱导液晶化合物的变温红外光谱研究

通过变温红外光谱研究了存在于４－［４－（２－氯－３－甲基丁酰氧基）－苯乙烯基］吡啶（ＭＢＳＢ）和对庚氧基苯甲酸（７ＢＡ）间的分子间氢键的稳定性及该氢键复合物的酯羰基基因与温度的依赖关系．结果表明，ＭＢＳＢ与７ＢＡ间的分子间氢键在液晶的清亮点以下具有良好的热稳定性．     

香豆素衍生物凝胶的制备及性质研究

设计合成了香豆素衍生物凝胶因子1,该凝胶因子可以在乙腈和N,N-二甲基亚砜(DMSO)中形成有机凝胶.通过紫外可见光谱(UV-vis)、红外光谱(FTIR)、扫描电镜(SEM)、X-射线粉末衍射(XRD)和接触角(CA)等技术对该凝胶因子在乙腈和N,N-二甲基亚砜的自组装过程进行了详细表征.该凝胶体系在氢键和范德华力的驱动力下自组装成微米带结构,该结构表面展示了疏水性质,其接触角为136.5°和124°.     

A supramolecular gel based on an adenine symmetrically grafted Anderson-type polyoxometalate complex

An Anderson-type polyoxometalate was covalently decorated by using adenine on both sides.Through cation substitution,we obtained a new hybrid building block with long alkyl chains for supramolecular gels.According to the synergetic effect of hydrogen bonding of inter adenine units and van der Waals interaction of side alkyl chains,the DODA 3 [A-MnMo 6-A] gelator can stabilize solvent and self-assemble into fibrous structure,forming supramolecular gel.In addition,the reversible sol-gel transformation was achieved by controlling environmental temperature.Scanning electron microscopy,transmission electron microscopy and X-ray diffraction were used to characterize the gel morphology and structure.As a result,we proposed the possible mechanism of gel formation and sol-gel transformation.     

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.     

Evidence of Hydrogen Bonding in Chloroform and Polyacrylates from NMR Measurements

IntroductionHydrogen bonding in polymer solutions hasattracted particular attention in recent yearsbecause of its importance in the understanding ofintermolecular interactions,which often affectphysical properties of polymer mixtures[17] .Studies have indicated that hydrogen bondingaffects the phase equilibrium behavior[8] ,e.g.,chloroform shows abnormal thermodynamicproperties in its vapor pressure,as well as in theheat and the volume of mixing with poly( propylene glycol dimethyl ether) [9] …     

Kaolin-based geopolymers with various NaOH concentrations

Kaolin geopolymers were produced by the alkali-activation of kaolin with an activator solution (a mixture of NaOH and sodium silicate solutions). The NaOH solution was prepared at a concentration of 6–14 mol/L and was mixed with the sodium silicate solution at a Na₂SiO₃/NaOH mass ratio of 0.24 to prepare an activator solution. The kaolin-to-activator solution mass ratio used was 0.80. This paper aimed to analyze the effect of NaOH concentration on the compressive strength of kaolin geopolymers at 80℃ for 1, 2, and 3 d. Kaolin geopolymers were stable in water, and strength results showed that the kaolin binder had adequate compressive strength with 12 mol/L of NaOH concentration. When the NaOH concentration increased, the SiO₂/Na₂O decreased. The increased Na₂O content enhanced the dissolution of kaolin as shown in X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) analyses. However, excess in this content was not beneficial for the strength development of kaolin geopolymers. In addition, there was the formation of more geopolymeric gel in 12 mol/L samples. The XRD pattern of the samples showed a higher amorphous content and a more geopolymer bonding existed as proved by FTIR analysis.     

超分子C14H14N4O8的合成及结构表征

以反丁烯二酸和咪唑为原料,采用缓慢蒸发溶剂法合成了新的有机加合物C14H14N4O8,并获得了其单晶体.通过红外、热化学分析、X-射线单晶衍射等技术对该加合物进行了结构测定和性质表征.晶体中分子通过分子间氢键相互连接构成超分子网络结构.该加合物属于三斜晶系,P-1空间群,a=0.746 77(15), b=7.736 3(15),c=8.405 5(17),α=69.73(3)°,β=80.40(3)°,γ=66.19(3)°,Z=1,V=416.75(14)A3,D=1.468 (mg/m3),F(000)=190.     

羧甲基纤维素与聚乳酸之间相互作用的光谱法研究

应用共振光散射光谱(RLS)、荧光光谱,并结合红外光谱,探讨了羧甲基纤维素(CMC)与聚乳酸(PLA)在溶液中的相互作用机理。结果表明CMC和PLA可以通过相互作用的氢键而形成稳定的分子间复合物(IPCs)。基于RLS技术详细讨论了CMC与PLA的质量比对其相互作用的影响。特别地,通过分析体系RLS信号强度的变化趋势,直观考察了CMC与PLC在溶液中相互作用过程。同时,基于RLS数据,利用自建模型计算了CMC与PLA之间的平均结合位点数。     

4-氨基安替比林电子光谱及溶剂效应理论研究

采用含时密度泛函理论方法(TD-PBE0)研究了4-氨基安替比林(4-AAP)在水和乙醇溶液环境中的电子光谱特性,通过电子跃迁轨道分析归属了4-AAP电子光谱谱带的跃迁轨道贡献并探究了其电子跃迁特征。研究结果表明,4-AAP在乙醇溶液中理论吸收谱带与实验谱带吻合较好,但其在水溶液中计算所得吸收谱带波长与实验所得相应值相差较大,溶剂水分子可与4-AAP通过氢键强烈相互作用形成复合物,诱导电子跃迁吸收谱带发生明显移动,氢键结合位点对其电子光谱中的最强吸收峰位置亦有影响,呈现显著的溶剂化效应。分子动力学模拟获得了水溶液中4-AAP溶剂团簇模型4-AAP-(H_2O)_3,基于此模型所得的理论电子光谱吸收谱带与实验光谱特征谱带波长相吻合,并从分子水平上对团簇结构吸收谱带的电子跃迁贡献进行了分析和归属。     

Preparation and characterization of chitosan/carboxymethylated konjac glucomannan blend films

In order to improve the mechanical and water swelling properties of the chitosan (CS) film, a series of transparent films were prepared by blending 2% (weight) chitosan acetic acid solution with 1.5% (weight) carboxymethylated konjac glucomannan (CMKGM) aqueous solution according to predetermined ratio and drying at 30°C. The morphological structure, miscibility, thermal stability, mechanical properies, and swelling capacity of the blend films were studied by infrared (IR), X-ray diffraction (XRD), differential thermal analysis (DTA), scanning electron micrograph (SEM), and measurements of the mechanical properties and swelling properties. The results demonstrated that there was strong interaction and good miscibility between CS and CMKGM resulted from intermolecular hydrogen bonding and electrostatic force. The mechanical properties in dry state and wet state, thermostability, and water swelling properties of the blend films were obviously improved. The best values of the tensile strength in the dry and wet state achieved 89 MPa and 49 MPa, respectively, when the CMKGM content was 30% (weight). The CS/ CMKGM blend films provided promising biomedical applications. Foundation item: Supported by the National Science Foundation of China (No.29977014). Biography: Zheng hua (1965-), male, Associate professor, research direction: renewable resource chemistry.