基于柱[5]芳烃和双醛淀粉的聚合物材料的制备及其对孔雀石绿的吸附研究

以双醛淀粉(DAS)为原料,利用氨基功能化的柱[5]芳烃(P[5])和1,6-己二胺作为交联剂,通过席夫碱反应制备了一种新型淀粉基聚合物材料(P[5]+C6-DAS)。吸附实验结果表明,相对于DAS,P[5]+C6-DAS对孔雀石绿(MG)具有更快的吸附动力学和更高的吸附容量。在100mg/L的条件下,P[5]+C6-DAS可在45min内去除94.4%的MG染料。此外,其吸附过程符合准二级吸附动力学模型和Langmuir等温吸附模型,最大吸附量可达3470.2mg/g。因此,P[5]+C6-DAS是一种具有潜在应用价值的MG染料吸附剂。

Pillar[5]arene based artificial light-harvesting supramolecular polymer for efficient and recyclable photocatalytic applications

Photosynthesis is the process through which living plants utilize photosynthetic pigments,such as chlorophyll,to convert CO_(2)and water into organic compounds and release O_(2)under visible light.In this study,we have successfully constructed a fluorescent supramolecular polymer(P5Py_(2)/Zn/Gen)n by employing orthogonal pillar[5]arene-based molecular recognition and metal ion coordination.Within the supramolecular polymer,the guest molecule Gen unit acts as a light-harvesting moiety,as the ACQ effect is inhibited by host-guest interactions,while the(Py)_(2)/Zn center serves as a catalytic site.By employing this orthogonal self-assembly strategy,we have enhanced the stability of both the donor and acceptor in catalyzing the reduction of p-nitrophenol to p-aminophenol.Moreover,this photocatalyst can be reused at least 5 times without significant conversion loss.These findings provide a pathway for constructing a recyclable artificial LHS that mimics the entire photosynthesis process.

Selective synthesis and physical properties of a bismacrocycle:Cycloparaphenylene-pillar[5]arene

Macrocyclic materials have attracted much attention due to their particular chemical and physical properties.Herein we report the precise synthesis and characterization of a new bismacrocycle structure base on cycloparaphenylene(CPP)and pillar[5]arene,named cycloparaphenylene-pillar[5]arenes(CPPn[5]).The bismacrocycle was fully characterized by NMR and HR-MS.The photophysical properties of CPPn[5]were investigated by UV–vis,and the maximum absorption peak was located at 331 nm,which was consistent with density functional theory(DFT)calculations.The fluorescence spectrum was further studied and the emission peak was maximized at 458 nm.The computational results indicate the strain energy of CPPn[5]is 27.80 kcal/mol and the HOMO-LUMO gap is 3.39 eV Notably,CPPn[5]showed interesting supramolecular properties.

A supramolecular oligo[2]rotaxane constructed by orthogonal platinum(Ⅱ) metallacycle and pillar[5]arene-based host–guest interactions

Oligo[n]rotaxanes are one of the most extensively studied categories of mechanically bonded macromolecules.In this study,a supramolecular oligo[2]rotaxane is successfully constructed driven by platinum(Ⅱ)metallacycle and pillar[5]arene-based host–guest interactions in an orthogonal way.The supramolecular oligo[2]rotaxane is further applied in fabricating a light harvesting system.

Supramolecular cyclization induced emission enhancement in a pillar[5]arene probe for discrimination of spermine

Early diagnosis and treatment of cancer requires the development of tools that are both sensitive and selective in detecting spermine.In this study,we presented a"supramolecular cyclization-induced emission enhancement"strategy for the sensitive and selective detection of spermine.A new pillar[5]arene probe(P1)demonstrated excellent solution/solid dual-state emission properties,and the addition of certain spermine(Spm)resulted in fluorescence enhancement due to the synergy of multiple weak interactions that restricted the free motion of P1 in the P1⊃Spm complex.This mechanism was further confirmed by time-resolved spectroscopy,DFT calculations,and IGM analysis.With its low limit of detection and high selectivity,P1 is a promising tool for measuring spermine in artificial urine samples.

Solvent and guest-binding-controlled chiroptical inversion of molecular devices based on pseudo[1]catenane-type pillar[5]arene derivatives

Four pillar[5]arene-based bicyclic compounds,so-called molecular universal joint(MUJ),were synthesized by incorporating a bisamide ring containing N,O,or S-heteroatom groups,which served as stimuli-responsive chiroptical molecular devices.The structure of MUJ was confirmed by 1H NMR spectra and single-crystal X-ray diffraction analysis,and their planar-chiral enantiomers were successfully separated.Chiroptical inversion behaviors from in to out configurations triggered by temperature,solvent,and guest complexation were investigated by circular dichroism spectra.Chiroptical inversion could be realized in the presence of adiponitrile in certain solvents due to the solvation effects on the side ring and the threading of the guest into the pillar[5]arene cavity.However,the stronger self-included interactions between the cavity and the inside ring of certain MUJs led to inhibition of the switching.

Insertion of pillar[5]arene into Troger’s base-derived porous organic polymer for promoted heterogeneous catalytic performance in Knoevenagel condensation and CO_(2)fixation

Development of new metal-free heterogeneous catalysts has long been the focus of intense research interest.The integration of multifunctional monomers into the skeletons of porous organic polymers(POPs)provides an efficient pathway to achieve this goal.Herein,we rationally designed and successfully prepared a new Troger’s base(TB)-derived POPs by insertion of pillar[5]arene macrocycle as a positively auxiliary group.Combined the both merits of pillar[5]arene macrocycle and TB moiety,the as-prepared polymer was further explored as an effective metal-free heterogeneous catalyst and exhibited promoted catalytic performance in Knoevenagel condensation and CO_(2)conversion.This work provides a new strategy to fabricate metal-free heterogeneous catalysts based on macrocyclic POPs.

Pillar[5]arene and Azine Derivative Assembly Improved Dual-Channel Detection of CN^(-)

The cyanide anion(CN^(–))is known to be one of the most toxic anions.Therefore,there is an urgent need to develop a reliable,sensitive,selective,rapid and effective method for the detection of CN^(–).Here,a self-assembly strategy based on pillar[5]arene P5 and azine derivative AZ was used to construct supramolecular sensors,and it was found that the detection effect of CN^(–)was significantly improved by the assembly strategy.The sensitivity of the assembled sensor P5-AZ to CN^(–)is more than 10 times higher than that of AZ.The detect mechanism was further investigated by theoretical calculations and 1H NMR.The results showed that AZ detects CN–by a deprotonation process with fluorescence enhancement,while P5-AZ improves the sensitivity of CN^(–)recognition through hydrogen bonding,anion-πand anion-dipole interactions,as well as the strong bonding ability of the assembly.Supramolecular assembly P5-AZ has the advantages of low toxicity,high sensitivity,and more importantly,it provides a method to detect CN^(–)sensitivity in the aqueous phase and organisms by host-guest assembly.

Water-soluble pillar[4]arene[1]quinone: Synthesis, host-guest property and application in the fluorescence turn-on sensing of ethylenediamine in aqueous solution, organic solvent and air

Water-soluble pillar[5]arenes are a class of typical macrocycles and have aroused tremendous attention for its easy to modify, abundant host-guest properties and extensive applications. However, up to now, all the reported water-soluble pillar[5]arenes acted as the host molecules, whereas they failed to be postsynthetically modified, which seriously impeded the development of the pillar[5]arene-based supramolecular chemistry. In this work, a new water-soluble pillar[5]arene, pillar[4]arene[1]quinone, was designed and synthsized with eight quaternary ammonium groups as well as a quinone units. Such a new water-soluble pillar[4]arene[1]quinone was capable of forming 1:1 stable complex with sodium 1-octanesulfonate in aqueous solution. Since the 1,4-quinone unit of WP[4]Q[1] could react with ethylenediamine (EDA) to form a conjugated quinoxaline structure, so pillar[4]arene[1]quinone could apply to the facile fluorescence turn-on sensing of EDA in aqueous solution, organic solvent and air.

基于柱[5]芳烃的超分子组装研究进展

介绍了柱[5]芳烃基于主客体性质和柱状立体结构的超分子组装,以及边缘取代基对柱[5]芳烃的溶解性、功能性和主客体性质的影响.

水溶性阳离子柱[5]芳烃还原石墨烯复合物在荧光检测左旋肉碱中的应用研究

采用湿化学还原法,在还原氧化石墨烯表面引入水溶性大环主体超分子柱[5]芳烃(CP5),形成复合物CP5-RGO。采用FTIR、XPS对复合物CP5-RGO进行表征。使用罗丹明123(R123)作为探针分子,CP5-RGO作为受体来构建荧光传感器,以此来检测左旋肉碱,其线性范围为0. 1～2. 0μmol/L和2. 0～25. 0μmol/L,检出限为0. 034μmol/L(S/N=3)。以牛奶为实际样品,采用加标回收方法探讨了R123@CP5-RGO传感器的实用性,其回收率为91. 0%～100. 2%,相对标准偏差(RSD)为2. 0%～2. 6%。所构建的荧光传感平台R123@CP5-RGO具有快速、灵敏、简便等优点,有望应用于实际样品的检测。

多孔柱[5]芳烃聚合物的制备及其对有机污染物的吸附性能研究

以柱[5]芳烃为单体,四氟对苯二腈为交联剂,制备一种新型多孔柱[5]芳烃聚合物吸附材料,具有高疏水性、富含电子空腔、更大比表面积,并对其进行FT-IR、13CNMR、BET等一系列结构性能表征,然后用于吸附一系列有机污染物,如双酚A、亚甲基蓝等,其吸附能力优异,且能快速吸附,并易于分离脱附。

直接甲醇燃料电池用Nafion~/柱[5]芳烃复合膜的制备及其性能研究

制备了一种新型Nafion~/柱[5]芳烃复合阻醇膜,通过傅里叶变换红外分析仪、核磁共振仪、扫描电子显微镜、热重分析仪等手段对柱[5]芳烃及复合膜的结构与性能进行了表征和测试。结果表明,该复合膜具有良好的热稳定性,较高的吸水率和较低的溶胀度;且柱[5]芳烃能有效地阻碍甲醇的透过,室温下甲醇渗透系数从Nafion~115膜的8.1×10^(-7)cm^2/s降低到Nafion~/柱[5]芳烃膜的2.1×10^(-7)cm^2/s;电流密度为65 mA/cm^2条件下,Nafion~/柱[5]芳烃复合膜的电池功率最高达到15.6 mW/cm^2,可用在直接甲醇燃料电池中。

还原氧化石墨烯-柱[5]芳烃-铂纳米粒子复合材料的制备及其应用

将带胺基的双亲柱[5]芳烃(AP5)修饰在还原氧化石墨烯(RGO)表面,得到水分散性RGO-AP5。用AP5做桥联剂,将预先制备的铂纳米粒子(PtNPs:Platinum Nanoparticles)自组装到RGO-AP5表面后得到三元纳米复合材料RGO-AP5-PtNPs。采用TEM、SEM、XRD等手段表征了复合材料的结构和形貌。考查了RGO-AP5-PtNPs中的三组分对客体分子在其修饰电极上的电化学响应的协同促进作用。

柱[5]芳烃对偶氮二异丁腈分子识别的研究及应用

以三氟化硼乙醚为催化剂、1,4-对甲氧基苯和多聚甲醛为原料合成具有高亲和性的全甲氧基柱[5]芳烃,通过核磁共振氢谱、紫外可见光谱、荧光光谱等检测手段研究了全甲氧基柱[5]芳烃对偶氮二异丁腈的分子识别能力。结果表明,全甲氧基柱[5]芳烃和偶氮二异丁腈可在氯仿中形成1∶1的主客体络合物,同时,全甲氧基柱[5]芳烃对偶氮二异丁腈具有刺激响应性,可作为荧光分子探针检测偶氮二异丁腈。

柱[5]芳烃及全衍生化合物的合成研究进展

柱芳烃是由对苯二酚醚或对苯二酚以亚甲基对位桥联的新型"柱"状大环超分子主体化合物、其结构对称、应用前景广阔。本文简述了柱[5]芳烃、全衍生化柱[5]芳烃的合成研究进展,并对它们的前景进行了展望。

阳离子化柱[5]芳烃改性沸石对溴甲酚紫的吸附研究

制备了阳离子化柱[5]芳烃改性沸石(CP5A/NZ),采用扫描电镜(SEM)、红外吸收光谱(IR)和X-射线粉末衍射(XRD)对CP5A/NZ进行表征,将其应用于阴离子染料溴甲酚紫(BCP)的吸附。考察了NZ粒径、改性时CP5A的浓度、吸附时间、BCP初始浓度和溶液pH值对BCP清除率的影响,分析了CP5A/NZ吸附BCP的动力学过程和吸附等温线,探讨了其吸附机制。SEM表征结果表明,经CP5A改性后,NZ具有的鳞片状结构消失,呈现体积增大的包块状结构;IR谱图中可以观察到CP5A/NZ中出现了CP5A中CH3N+和CH2N+的振动吸收峰;XRD揭示了NZ经CP5A改性后具有不同的晶体结构,上述结果均表明CP5A成功负载到NZ上。吸附研究结果表明,由于电荷斥力,NZ对BCP没有清除能力,但使用10 g/L的CP5A溶液改性粒径为0.42~0.59 nm的NZ时,其对BCP的清除率达94.0%,且吸附在300 min时达到平衡,而CP5A/NZ处理低浓度(<100 mg/L)BCP溶液时具有较高的清除率。二级动力学方程和Langmuir型等温线能更好地描述CP5A/NZ对BCP的吸附过程。推测CP5A/NZ对BCP的吸附机理为:CP5A中的CH2N+与NZ发生阳离子交换后, CH2N+与NZ表面的负电位点结合,使NZ表面的正电荷活性吸附位点增加,从而对阴离子染料BCP具有较好的清除能力。

基于水溶性柱[5]芳烃主体的合成及Ag^+识别性能研究

通过设计合成一种水溶性阳离子型柱芳烃季铵盐主体P,在柱芳烃主体的骨架苯环上引入了10个季铵盐基团.研究结果表明,在水溶性的阳离子柱芳烃季铵盐的水溶液中分别加入常见的金属阳离子(Pb 2^+、Cd 2^+、Ni 2^+、Co 2^+、Cr 3^+、Zn 2^+、Cu 2^+、Ca 2^+、Ag^+、Fe 2^+、Fe 3^+、Na^+、Hg 2^+、K^+和Mg 2^+)时,该水溶性柱芳烃主体能够选择性的在紫外光谱上识别Ag^+.且该水溶性柱芳烃主体对Ag^+的最低检测限可达到1.25×10^-5 M,络合常数为0.95×10^5 M^-1,这说明该水溶性柱芳烃与Ag^+之间的相互作用很强,对Ag^+具有良好的紫外选择性识别能力,可用作受体分子在纯水相中检测Ag^+.

柱[5]芳烃共价偶联聚乙二醇聚拟轮烷滑环材料的合成与流变性质

通过柱[5]芳烃与高分子量聚乙二醇共价交联构筑了系列互穿交联聚合物,经过退火制备了柱芳烃-聚乙二醇互穿滑环材料.核磁滴定实验、模型分子互穿实验以及高分子量聚乙二醇互穿等研究结果表明,在该聚合物中柱[5]芳烃与聚乙二醇发生晶态络合并达到互穿平衡. X射线粉末衍射及差示扫描量热-热重分析实验结果证实该互穿滑轮聚合物具有良好的晶型结构、热性能及热稳定性,由分子量为1×106的聚乙二醇合成的固态聚拟轮烷表现出较好的滑环效应,其流变行为受到链长度、滑环数量和滑环运动等因素影响.在引入滑环分子柱[5]芳烃后,该固体滑环材料表现出较好的热稳定性、柔性以及弹性机制响应性.

A pillar[5]arene-based side-chain pseudorotaxanes and polypseudorotaxanes as novel fluorescent sensors for the selective detection of halogen ions

A pseudorotaxane and its polypseudorotaxanes formed between pillar[5]arene moieties and noctylpyrazinium cations as novel fluorescent sensors for the selective detection of halogen ions were reported.A collapse of these pillar[5]arene-based pseudorotaxanes and polypseudorotaxanes occurred upon the addition of Cl,Br,and I（tetrabutylammonium salts）,respectively,leading to their fluorescence recovery.The fluorescence enhancement of the pseudorotaxane and the polypseudorotaxanes increases in the order of I