The Calixrene-type Imidazolium Cyclophanes:Synthesis,Crystal Structure And Its Recognition Activities For Nucletides

Nucleotides are very important anions in biological,they are the part of the structure of the DNA and RNA,they exsit in cells by free state and play a vital role in biological function.ATP,GTP,UTP are closely related in various life activities.Imidazolium cyclophanes have special cavity and the C(2)-H of imidazolium can form hydrogen bonds which can be optimized by modifying the cyclophanes.I report five series,a total of 10 kinds of imidazolium cyclophane with benzene,naphthalene,anthracene,biphenyl,acridine ring,which have structures characteristics of calixarene,and they were synthesized by multistep reactions with p-methyl phenol,p-tert-butyl phenol,imidazole,etc as main raw materials.The final structure of all related intermediates and target producs were cofirmed by IR?1H NMR?13C NMR?high mass spectrometry.The imidazolium compounds which was built by naphthalene and biphenyl ring was instability.The synthesis of these compounds appear exceptional condition.And we propose the possible reaction mechanism in this paper.I get the crystal structure of imidazolium cyclophanes 11,12,23,25 by solvent diffusion method and carry out the crystal structure by X-ray single crystal diffraction.The crystal structure show that the structures of these compounds are similar to cup shape of the calixrene,C(2)-H of the imidazolium and the phenolic hydroxyl stay in the same side of the ring flat,because of bezene ring linking to imidazolium ring by methylene,thereby the ?-bond can't rotate,leading to this structure of the imidazolium cyclophanes looks like trapezoid.The calixrene imidazolium cyclophane supramolecular recognition of Aden osine-5?-triphosphate(ATP),Adenosine-5?-monophosphate(AMP),Adenosine-5?-diphosphate(ADP),Guanosine-5?-triphosphate(GTP),Uridine-5?-triphosphate(UTP)are studied by fluorescence spectrometry.The results show that 11,12,14,23,24,25 all display fluorescence quenching when addition upon of ATP,GTP,UTP,AT,AMP,ADP.15,17 show fluorescence enhance to UTP,and show flurescence quenching to ATP,GTP,AT,ADP,AMP;16,18 show flurescence quenching to AT,and show fluorescence enhance to other guest molecules.Base on the experiment result of the fluorescence emission spectroscopy,we continue to investigate the changes in the absorption of calixrene imidazoli um cyclophane for guest molecules by UV –vis spectroscopy.After adding the host molecules 11,12,14,23,24,25,the absorbance of the guest mol ecule ATP decreases greatly.We speculate that the host molecules 11,12,14,23,24,25 have the best recognition of ATP.After addition of the host molecules 15 to 18,the absorbance of the guest molecules ATP,GTP,UTP,AT,ADP and AMP were increased,and the host-guest molecules formed t he supramolecular system in the recognition of the guest molecules ATP,U TP,AT,ADP and AMP.The maximum absorption wavelength of the guest molecule occurs blue shift.