Application Of Heterocalixaromatics On The Analysis Of Environmental Sample And Biological Fluids

Rapid separation and accurate determination of trace component in complexsystem is an important and difficult task that the analytical workers must be facedwith. As the sample system becomes more and more complex,the analyte becomeslower and lower,to develop a simple,efficient,fast,green and accurate technique ofsample separation and measurement has been an important research subject.As the third-generation supermolecules after crown ethers and cyclodextrins,calixarenes are quite good molecule platforms, the structures of which are easilymodified. As a kind of novel compound, heterocalixaromatics replaced the methylenebridge of the traditional calixarenes to nitrogen or oxygen atom and phenol groups ofcalixarene were replaced by aromatic heterocyclics(such as Triazine, pyridine, furan,thiophene,etc). Compared to the traditional calixarenes, heterocalixaromatics hadgreat changes in the structure, performance and molecular recognition.Heterocalixaromatics silica-bonded stationary phase had hydrophobic interaction、π-πinteraction、 π-electron transfer、 electrostatic interaction and hydrogen-bondinteraction. The synergy effect is greatly intensified for the selective and retentionability of the complex and special samples. This paper systematicially studiedheterocalixaromatics as liquid chromatographic stationary phase and solid phaseextraction material on the Environmental sample and biological fluids. This thesis ismainly divided into the following three parts.1. The silica-boned tetraoxocalix[2]arene[2] stationary phase (TOA2T2) was appliedto determinations of chlorantraniliprole in soil by HPLC-UV. The result aresatisfactory with a good linear ralationary in the range of0.5～5μg/mL(R2=0.9995), good reproducibility (peak area RSD=1.91%),detectionlimit1.27ng/mL,recoveries80.2～100.3%.2. Study a new type of NCS-SPE-UPLC-MS/MS for detecting eight heterocyclicamine in the human urine. The result are satisfactory with a good linearralationary in the range of0.05-100ng/mL(R2≥0.994), detection limit was in 0.82-2.25pg/mL, quantitative limit was in2.75-10.8pg/mL. Using thelaboratory-made solid-phase extraction packing separated and enriched eightheterocyclic amine in the human urine. Although individual heterocyclic amineshad low recovery rate, this method offers a new method for separation andenrichment of heterocyclic amines.3. Six heterocyclic amines were analyzed by the method based on ecectrosprayionization tandem mass spectrometry(ESI-MSn). The fragmentation patterns ofsix heterocyclic amines in positive mode haved been summarized. The resultscould save time and material consuming efforts in structure identification andtraditional phytochemistry analyses compound of this species.