| Objective:Anions widely exist in the fields of chemistry,biology,medicine,and environmental processes.For example,amino acids,peptides,and nucleotide salts in organisms are all anions,and many inorganic anions such as fluoride,phosphate,sulfate and chloride.A large number of them exist in industrial production and the environment.At the same time,some important anions also play a variety of roles.Carboxylic acid anions are also an important type of biologically related anions,which appear in metabolic pathways,such as the Krebs cycle and fatty acid metabolism.The development of new sensor systems that recognize important biological anions has attracted considerable attention.Tartaric acid is widely distributed in nature,especially in grape juice.Only a single optically active tartaric acid or racemic tartaric acid can be separated before it can be safely used in the food and pharmaceutical industries without causing harm to life.Methods:In this thesis,12 intermediates and 10 anion receptors were designed and synthesized,of which 5 were chiral receptors.In addition,4 metal anion ligands were synthesized.1H-NMR,13C-NMR,UV-vis,HR-MS and other analytical methods were used to characterize the synthesized compounds;nuclear magnetic resonance spectroscopy,ultraviolet-visible absorption spectroscopy,fluorescence spectroscopy and other detection methods were used to study these receptors against guest anions.In addition,the recognition performance of the target compound on the optically active carboxylic acid can be investigated by the circular dichroism(CD)method.Job curve method is used to determine the stoichiometric ratio of the host and guest.Then DFT is used to simulate the structure and conformation of the host-guest combination complex.Conclusion:This thesis is divided into four chapters,the main contents are as follows:1.Summarize the necessity of designing anion chemical sensors,introduce some chemical sensors for inorganic anions and carboxylic anions,and put forward the design ideas of this paper on this basis.2.The target receptor molecules Ⅱ-1,Ⅱ-2,Ⅱ-3,Ⅱ-4 were synthesized by reacting n-octylamine,benzylamine,2-aminomethylpyridine and optically active pyridine amine with m-phenyl-bridged dipyrrole dialdehyde respectively.Ultraviolet spectroscopy and circular dichroic spectroscopy were used to investigate the recognition performance of the host to the guest monocarboxylic acid anion and dicarboxylic acid anion.The host and guest interact through multiple hydrogen bonds,and the titration graph and the job graph prove that the host and guest form a 1:1 complex.Receptor Ⅱ-3 has a configuration flipping phenomenon for dicarboxylic acid anions such as dibenzoyl tartaric acid(DBTA),tartaric acid(TA)and malic acid(Mal),while with monocarboxylic acid mandelic acid,there will be no configuration.Flip.The calculation of the binding constant shows that the receptor 11-2 has the highest intensity when compared with Ⅱ-1,Ⅱ-3 and Ⅱ-4 when it interacts with DBTA and MA,and the receptor Ⅱ-1,11-2,Ⅱ-3 and Ⅱ-4 shows good enantioselectivity to mandelic anion.3.In this chapter,n-octylamine and 2-aminomethylpyridine are used to obtain acceptor molecules Ⅲ-1 and Ⅲ-2 containing schiff base structural units through condensation with p-phenylenedipyrrole dialdehyde respectively,plus the above synthesized Ⅱ-1,11-2,11-3,Ⅱ-4 four compounds,through fluorescence spectroscopy,ultraviolet-visible spectroscopy,the selective recognition performance of these six acceptors to guest inorganic anions,found that the end is connected with an electron donor.The receptors Ⅱ-1 and Ⅱ-4 of the effective aliphatic chain have wider selectivity for anions,while the receptors Ⅱ-2 and Ⅱ-4 of the aromatic ring with electron withdrawing effect at the end have better single selectivity for anions.With the help of fluorescence spectroscopy,the change of the solvent on the fluorescence intensity of the host Ⅲ-1 was investigated,and it was found that the solvent effect had a great influence on the fluorescence color and intensity.Through preliminary experiments on the selectivity of anions,it is found that Ⅱ-3 has significant selectivity to HSO4-,and then through the quantitative titration experiment of HSO4-in Ⅱ-3,the job-plot experiment of Ⅱ-3 and HSO4-,it is confirmed the stoichiometric ratio of the two is 1:1,and the possible combination mode of the two is simulated.4.The ligands Ⅲ-3,Ⅲ-4,Ⅱ-5,Ⅱ-6 were synthesized by the reaction of p-phthalopyrrole dialdehyde and isophthalopyrrole dialdehyde with two optically active amines and reacted with Pd(OAc)2.The metal-organic-one-dimensional coordination polymer Ⅲ-3-Pd,Ⅲ-4-Pd,Ⅱ-5-Pd,Ⅱ-6-Pd.The spectral characteristics of the compounds were studied by ultraviolet-visible spectroscopy and circular dichroic spectroscopy.And through the circular dichroic spectrum,it is found that the two pairs exhibit a perfect mirror symmetry relationship with each other,and the respective configurations can be easily distinguished.In addition,the structure,molecular weight and molecular weight distribution of the polymer were characterized by proton nuclear magnetic resonance spectroscopy(1H-NMR)and gel permeation chromatography(GPC).The obtained results indicate that the prepared polymer has a clear structure.And it was found that polymerⅢ-3-Pd can be used as a good probe for CN-recognition. |
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