Spectral Characteristic Of The Supramolecular Assembly And Recognition Of Amphiphlic Calix[4]Resorcinarenes

Supramolecular chemistry is an important research field in current chemistry.System based on calixarene plays an important role in the field of supramolecularchemistry. A series of amphiphilic benzodiazepines calixarene were synthesized andtheir binding behaviors to the fluorescent guests were also investgated in differentsolvents were studied. Following are the main contents:A series of calix[4]resorcinarenes (CRA) were synthesized with Resorcinol andfatty aldehyde. Then a series of derivatives such as ether ester (CRE), carboxylic acid(CRC) and sulfonic acid type (CRS) were obtained. Their structures were confirmedby FTIR and1HNMR et al. The solubility, spectral characteristic and surface activityof the CRS were also studied and CRS in aqueous solution were fluorescent andemitting wavelength changed by varying the exited wavelength or concentration ofthe CRS solutions.Aggregation properties of water-soluble dye in chloroform were studied in thepresence of Resorcinarenes by two-phase extraction technology. CRA and CRE canencapsulate only cationic dyes. The loading ability of C11CRA, C6CRA and C6CREto MB is different. Each C11CRA, C6CRA and C6CRE can encapsulate about2.5,2and0.5MB molecules. There were competitive or synergistic effects betweendifferent pair of dyes. When MB and AO exist at the same time, there is priorityselectivity in encapsulation for C11CRA to AO and load ability to MB decrease withexistence of AO. But the presence of MB molecules almost has no influence onencapsulation of C11CRA to AO molecules. When the dye pairs are MB and RhB,encapsulation capacity of C11CRA to both dyes decreased. For MB and MO, they canform a complex dissolved in CHCl2or when mixed together and the presence ofC11CRA can increase the possibility of MB and MO transfer from aqueous solutionto CHCl3phase. When MB and FSS mixed together, FSS can not be transferred toCHCl2phase and the existence of FSS decreased the encapsulation of C11CRA toMB.Four complexes including C6CRA-HPEI, C11CRA-HPEI, C6CRE-HPEI andC11CRE-HPEI were constructed with Resorcinarenes and HPEI. Encapsulationcapacity of complexes improved remarkably compared with HPEI itself. They stillhave the ability to form complex with HPEI after their saturated encapsulation withMB and the complex also have ability to interact with MO. Influences of two water-soluble calixarene on the thiazole orange cyanine dyeswere studied. Stoichiometric ratio of calix [6] arene and dyes was1:1. Solubility ofdyes in water was improved, which made it a potential fluorescent probe asbiomarkers. While the interaction of C6CRS with thiazole orange cyanine (TO) wasquite different. The stoichiometric ratio between C6CRS and TO was1:4. Addition ofmetal cations may have competitive effect with TO-COOH to interact with C6CRS.The higher the valence of cations, the more significant fluorescence intensity changesof the complex. In protein labeling experiments, TO-C6CRS had advantages overTO-COOH itself. While protein labeled with C6CRS itself achieved good result,which suggested that C6CRS can improve solubility of TO in water and used as apotential fluorescent probe to label protein.The interactions between three water-soluble dyes of RhB, AO, FSS and C6CRSwere studied. There was quenching effect between C6CRS and dyes. Thestoichiometric ratio of C6CRS and three dyes had the same values of1:4, whichsuggested that electrostatic attraction between C6CRS and dyes is not dominant roleand the principal pi-pi stacking may account for this. For comparison, we chose toinvestigate interaction between a sulfonated Gemini surfactant and RhodamineB/acridine orange. Results showed that the dyes involved in the process of the micelleformation and the size of the dyes had different effect on the aggregation properties ofGemini surfactant. When the AO and RhB coexisted in the solution of Geminisurfactant, energy transfer from AO to RhB was observed.