Design,Synthesis and Molecular Recognition Properties of Functional Calixarene (Pillarene) Assembled Graphene

Author:Mao Xiao Wei

Supervisor:li hai bing

Database:Doctor

Degree Year:2014

Download:24

Pages:141

Size:18364K

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Developing highly sensitivechemical sensorfor important bioactive substances in complex biological fluids remains a great challenge task.Due to the unique nanostructure and extraordinary properties,graphene have shown promising applications in the construction of high performance electrochemical sensor and fluorescent sensoretc.However,material availability and processability will be the rate-limiting steps in theevaluation of extensive applications of graphene.To endow graphene with sensing capabilities,it is oftennecessary to functionalize it with recognition elements thatbring the detection targets onto the graphene surface throughspecific interactions and sometimes also assist in signal transduction.Calixarene(pillararene),with itsunique structure,molecular recognitionandversatile functionalitycharacteristics,offer the possibility for the surface modification of graphene.This thesis is focused on fabricating the designed and synthesizedcalixarene(pillararene),served as a recongition unit,and immobilizingthem onto graphene.Their potential applications in molecule recognitionin the complex biological samples were also discussed.The combination of the excellent properties of graphene and the molecular recognition ability of calixarene(pillararene)to design intelligent sensing system has contributed to creating a variety of efficient,sensitive,convenient sensing system.The main contents are shown as following:1.The properties and applications of graphene were outlined.The unique structure and characteristics of calixarene(pillararene)were introduced.On the basis of the above review we put forward our design ideas and research topics.2.Calix[4]arene was covalently modified with pyreneto producecalix[4]arene triazole-linked pyrene derivatives(CP),which was further modified on graphene(CP-G)through π-π reaction to obtain a complexed highly senstitve sensor.Notably,taking both advantages of functional calixarene and graphene,the proposed CP-G not onlydemonstrates extremely high sensitivity and selectivity toward recognition of carbaryl in serum with a detection limit at nM level,but a visiblemacroscopicresponsivewettabilityvariation was also realized here.3.R-mandelic acidcalix[4]arene was designed andsynthesied for modification of graphene via clicked reaction,which provided as an efficient chiral discriminationfor amino propanol enantiomers.Notably,taking both advantages of functional calixarene and graphene,the proposed FC4D-G not only demonstrates extremely high sensitivity and selectivity toward recognition of amino propanol enantiomers in serum with a detection limit at nM level,but a visible macroscopic chirality-responsive wettability variation was also realized here.4.A β-cyclodextrin modified graphene oxide system was reported,which provided a new enantioselective sensing device for amino acid enantiomers both in vitro and in living cells.The excellent sensing capabilities of this functional graphene oxide in living cells shown here make it a robust candidate for many biological fields,such as intracellular imaging,and intracellular tracking,etc.5.p-Sulfonated calix[6]arene modified graphene has been firstlysynthesized and provided as a ’turn on’ probe for carnitinethrough monitoring the fluorescence signal both in vitro and inliving cells.6.Hydrazino-linkedpillar[5]arene modified graphene has been firstlysynthesized and provided as a ’turn on’ probe for paraquat detection through monitoring the fluorescence signal both inliving cells and mice.7.Naphthol-linkedpillar[5]arene modified graphene,served as anarginineresponsive wettability switch surfacehas been firstlysynthesized,provide ascontrolled release biosurface for Hela cells.