The Construction And Property Of Bi-omponent Supramolecular Gel Based On Amide/Imide And Pillararene

Supramolecular gels as a class of smart materials,which have attracted wide attention because of potential applications in chemical sensing,biological materials,separation,surface science,drug delivery and gas storage.It is reported that the great majority supramolecular gels contain only one kind of gelator,and supramolecular gels were constructed with two or more kinds of gelators will greatly enrich the development of supramolecular gels.Hence,the research on bi-component supramolecular gels provides good opportunities for the development of ion selective detection and removal of materials.In view of this,the design strategies of this thesis are as following.Firstly,in order to improve the assembly ability of supramolecular gels,the tripodal pyridylamide structure was introduced into the first kind of gelator,which possess multiple assembly sites including hydrogen bond and?-electron acceptors etc.Secondly,to obtain supramolecular gels with ions'fluorescence colorimetric detection function,naphthalimide moiety was introduced into the second kind of gelator,which could serve as good fluorescent groups and also act as?-electron donors.Thirdly,pillar[5]arene serves as a new generation of macrocyclic host,has electron-rich cavity and easy to functionalize property etc.,which provides good site for the detection of ions.So,this thesis also employed functionalized pillar[5]arene derivertive as the third kind of gelator.In this thesis,a variety of bi-component supramolecular gels were constructed by pairwise coupling assembling of these gelators.Then,the ion recognition and separation properties of the obtained gels were studied.The obtained gel materials could be used for the detection and removal of metal ions in water;meanwhile,these materials have potential application value in stimuli-responsive smart materials.This thesis is divided into four chapters,the specific contents are as follows:Chapter 1:The research progress of supramolecular gels based on tripodal pyridylamide,naphthalimide,pillar[5]arene,single-component,bi-component and multi-component are introduced,respectively.On the basis of these background studies,the research topics of this thesis are summarized and proposed.Chapter 2:The bi-component supramolecular gel?RQ?was successfully constructed by the assembly of the gelators N-?4-amino-phenyl?naphthalimide?R?and tripodal pyridylamide?Q?in DMSO-H₂O?6.1:3.9,v/v?binary solution.The gel RQ exhibited excellent self-healing capacity.Interestingly,the RQ could fluorescently detect and reversibly remove Hg²⁺from water through cation-?interactions with the merits of high selectivity,efficient adsorption and quick response.The limit of lowest detection?LOD?of the RQ for Hg²⁺was 4.52×10^-8 M and removal rate was 91.14%.Moreover,the RQ could be efficiently recycled and regenerated with little loss via a simple treatment by I^-.Notably,the thin films based on RQ and RQ+Hg²⁺were prepared,which could serve as convenient and efficient test tools for detection of Hg²⁺and I^-,respectively.This work provided an efficient method for separation and detection of Hg²⁺.Chapter 3:An easily prepared bi-component supramolecular hydrogel with strong aggregation-induced emission?AIE??MQ-G?was successfully constructed by the gelators Schiff-base functionalized naphthalimide?M?and tripodal pyridylamide?Q?in DMSO-H₂O?6:4,v/v?via?-?,hydrogen bond and?-electron donor-acceptor interactions.The MQ-G showed excellent self-healing property and strong orange AIE.The fluorescence quantum yield of the MQ-G was measured as 57.8%.Moreover,the MQ-G could successively sense Fe³⁺and H₂PO₄^-in water through a fluorescent"ON-OFF-ON"pathway,which suggests the MQ-G could serve as an"ON-OFF-ON"fluorescent material and efficient logic gate.Meanwhile,the xerogel of MQ-G was capable of removing Fe³⁺at an adsorption rate of 99.72%from diluted aqueous solution.Moreover,the thin films based on the MQ-G and MQ-G+Fe³⁺were also prepared,which could not only act as supramolecular fluorescent material but serve as simple and efficient tool for detection Fe³⁺and H₂PO₄^-,respectively.Chapter 4:A novel supramolecular hydrogel?TP-QG?has been successfully constructed via the assembly of the gelators functionalized pillar[5]arene?TP?and tripodal pyridylamide?Q?in DMSO-H₂O?6:4,v/v?binary solution.The obtained TP-QG showed excellent self-healing property and multi-stimuli responsive behavior,such as thermal-responsiveness,ion-responsiveness,pH-responsiveness and competitive guest-responsiveness,etc.Interestingly,the TP-QG exhibited strong AIE effect.The TP-QG could successively fluorescence detect Fe³⁺and F^-in water via fluorescent"ON-OFF-ON"pathway,the TP-QG could serve as an"ON-OFF-ON"fluorescent material and efficient logic gate.The limit of lowest detection?LOD?of the TP-QG for Fe³⁺was 2.32×10^-10 M.Meanwhile,the xerogel of the TP-QG could remove Fe³⁺from water,and the adsorption ratio was 98.68%.Moreover,the xerogel of the TP-QG-Fe could remove F^-by ion chromatography?IC?analysis in water,the removal ratio about87.92%.In addition,the thin films based on the TP-QG and TP-QG-Fe were prepared,which could be act as convenient test tools for detection Fe³⁺and F^-,respectively.Notably,the TP-QG and TP-QG-Fe also show conductive properties and could be used as conductive materials,respectively.