以瓜环为主体的新型轮烷的合成及性质研究

【作者】 王海燕；

【导师】 肖昕；

【作者基本信息】 贵州大学 ， 应用化学， 2019， 硕士

【摘要】 超分子化学是利用非共价键之间的相互作用力来形成的超分子组装聚集体。瓜环（Q[n]）作为超分子化学领域中的一种重要的主体化合物,因其在两端的亲水性端口和疏水性空腔的独特结构,可以在溶液中选择性地结合多种有机、无机及生物分子形成主-客体包结配合物或自装超分子实体。以瓜环为基本构筑单元,在溶液中加入小分子化合物或其他与瓜环结构相匹配的化合物等,利用分子间弱的非共价键相互作用力,可以得到各种基于瓜环的超分子化合物,使其在很多领域中都有着潜在的应用价值,并在材料科学、生物科学、物理学、信息科学等不同领域都具有潜在的应用前景。本论文选择了一系列吡啶乙烯衍生物,苯并吲唑衍生物,联二萘酚衍生物以及卡培他滨分子,以此为轴分子研究其与瓜环自组装形成的轮烷性质,应用核磁共振技术、等温量热滴定、紫外吸收光谱、荧光光谱、质谱等物理化学方法对其自组装体系的性质进行了研究。实验内容及结果研究如下:（1）合成吡啶乙烯类衍生物（G1、G2、G3）,选择七元瓜环与之进行超分子轮烷自组装,在水溶液中运用紫外-可见吸收光谱、荧光光谱、等温滴定量热分析、基质辅助激光解吸电离飞行时间质谱、动态光散射以及核磁共振技术等手段研究了其与主体分子Q[7]之间的相互作用,实验结果表明:在G1和G2中,七元瓜环与客体分子具有两种相同的作用模式,当N_Q[7]/N_{（G1、G2）}=2:1时,2个七元瓜环包结在客体分子的烷基链上,形成类似哑铃形状的[3]轮烷模式,当N_Q[7]/N_{（G1、G2）}=3:1时,2个七元瓜环包结在客体烷基链上,同时第三个瓜环包结在母体乙烯吡啶上并在其上来回移动,形成[4]轮烷模式;在G3中,当N_Q[7]/N_G3=2:1时,形成与前两种作用模式相同的[3]轮烷模式,但之后却不会形成[4]轮烷模式,而是当N_Q[7]/N_G3=4:1时,形成[5]轮烷模式。该表明结果通过控制瓜环的量,可以进行轮烷结构的调控。（2）合成了苯并吲唑类衍生物DIHY,选择Q[8]、Q[7]、TMeQ[6]作为主体分子,运用紫外-可见吸收光谱、荧光光谱、等温滴定量热分析、基质辅助激光解吸电离飞行时间质谱及核磁共振技术（¹H NMR,2D NMR,DOSY）等手段研究了其与客体分子的相互作用模式,这三种具有不同空腔大小的瓜环与DIHY之间具有不同的作用模式。研究结果表明:TMeQ[6]-DIHY体系中,客体分子位于瓜环的端口处;Q[7]-DIHY体系中,客体分子DIHY的4,5-二氢-2H-苯并吲唑部分进入到瓜环的空腔内部,而吡啶基团位于瓜环的端口形成1:1的类轮烷结构,Q[8]-DIHY DIHY体系中2个客体分子DIHY的4,5-二氢-2H-苯并吲唑部分以“面对面”的堆叠方式进入进入到Q[8]的空腔中,而吡啶基团位于瓜环的端口而吡啶基团位于瓜环的端口,自组装形成1:2的超分子结构,可见不同聚合度的瓜环,与DIHY形成了不同作用模式的组装体。（3）以卡培他滨作为客体分子,以iQ[7]和Q[7]为主体分子使之其与客体在水溶液中相互作用,利用紫外-可见吸收光谱、荧光光谱、等温滴定量热分析、基质辅助激光解吸电离飞行时间质谱及核磁共振技术等手段研究了其相互作用模式,研究发现瓜环包结在客体的烷基链部分,形成1:1的类轮烷自组装。（4）以S/R型联二萘酚为母体,合成具有pH响应的轴分子,以七元瓜环为主体分子,运用紫外-可见吸收光谱、等温滴定量热分析、基质辅助激光解吸电离飞行时间质谱、核磁共振技术及圆二色谱等技术手段探究相互作用模式。实验结果表明:在中性或酸性环境中,Q[7]与联二萘酚以2:1的方式作用在联二萘酚的烷基链部分,而当pH>8时,Q[7]与联二萘酚以1:1的方式作用在联二萘酚的吡啶乙烯部分。实验通过调节pH值来调控瓜环在轴分子上的作用位点。更多还原

【Abstract】 Supramolecular chemistry is a supramolecular assembly of aggregates formed by the interaction forces between non-covalent bonds.The Cucurbit[n]urils(Q[n])is an important host compound in the supramolecular chemical.Because of its unique structure,which has a hydrophobic cavity with two opening portals rimmed with identical carbonyl groups,it can selectively bind Organic,inorganic,and biomolecules in solution to form host-guest inclusion complexes or self-assembly supramolecular compound.Cucurbit[n]urils has been used as the basic building unit to band small molecule or other compound matching the structure of cucurbit[n]urils for constructing various cucurbit[n]urils-based supramolecules by using weak non-covalent bond interaction forces.Those compounds have potential application value in many fields,and have potential application prospects in different fields such as materials science,biological sciences,physics,and information science.In this thesis,a series of pyridyl ethylene derivatives,benzoxazole derivatives,bis-naphthol derivatives and capecitabine drug molecules were selected to study the properties of rotaxane formed by self-assembly of guest molecule and cucurbit[n]urils.The properties of self-assembly system were studied by NMR,isothermal calorimetry,ultraviolet absorption spectroscopy,fluorescence spectroscopy,mass spectrometry and other physical and chemical methods.The experimental contents and results are as follows:A series of pseudorotaxanes in water based on Q[7]and bispyridinium ethylene-decane-imidazole with different lengths of aliphatic chains as an axle was synthesized,and explored their properties using ~1H NMR,UV and fluorescence spectroscopies,mass spectrometry,and DLS.the mode of action of pseudorotaxanes could be controlled by changing the amount of Q[7],and the alkyl chain attached to the imidazole nitrogen could also influence the mode of pseudorotaxanes.For G1 and G2 systems,increasing the amount of Q[7]altered the host-guest interaction from a dumbbell-shaped structure([3]pseudorotaxanes)to a[4]pseudorotaxane structure.For the G3 system,increasing the amount of Q[7]changed the dumbbell-shaped structure into a[5]pseudorotaxane structure.This indicated that the alkyl chain attached to the imidazole nitrogen could also influence the mode of pseudorotaxanes.A pharmaceutical intermediate,3-pyridyl benzoxazole derivatives(DIHY),was designed and synthesized as the guest molecule.The self-assembly binding models of tetramethyl cucurbit[6]uril(TMeQ[6]),cucurbit[7]uril(Q[7])and cucurbit[8]uril(Q[8])with DIHY were investigated by ~1H NMR,MS,Isothermal Titration Calorimetry and UV-vis spectrum.The results showed that there are different modes of interaction between these three different cucurbit[n]uril and DIHY.For the TMeQ[6]-DIHY system,the guest molecule is located at the port of the TMeQ[6],while for the Q[7]-DIHY system,the 4,5-dihydro-2H-benzoxazole moiety of the guest molecule reside within the cavity of the Q[7]host,whereas the pyridyl group of DIHY guest remains outside of the portal to form the 1:1 inclusion complexes of pseudorotaxane structure.Nevertheless,the 4,5-dihydro-2H-benzoxazole moiety of two guest molecule is included in the cavity of the Q[8]host in a“face to face”stacking way,while the pyridine group of DIHY is located at the port of the Q[8]to form a 1:2supramolecular structure.The host-guest interaction between capecitabine and i Q[7]/Q[7]was studied by using UV-visible absorption spectroscopy,fluorescence spectroscopy,MALDI-TOF MS and ITC.and the experimental results reavled that iQ[7]/Q[7]was encapsulated into the alkyl chain part of the guest to form a 1:1 pseudorotaxanes structure.Using S/R bis-naphthol as the basic unit,a axle molecule with pH response was synthesized.The interaction mode of Q[7]-R-BNH/S-BNH was explored using UV-visible absorption spectroscopy,isothermal titration calorimetry,matrix-assisted in aqueous solution.MALDI-TOF mass spectra,nuclear magnetic resonance spectroscopy and circular dichroism techniques.The experimental results showed that when the external environment is neutral or acidic,the alkyl chain portion of the binaphthol derivative is included in the cavity of the Q[7]in a 2:1 portion.While pH>8,the pyridyl group of the binaphthol derivative is located in the cavity of the Q[7]in a 1:1 portion.It is possible to control the action site of the cucurbit[n]uril on the axis molecule by regulating the pH.更多还原