Several new nitrogen-containing calixarene derivatives have been synthesized and their ion-binding properties investigated by UV spectroscopy and solvent extraction. These derivatives include 5,11,17,23-tetra-t-butyl-25,26,27,28-tetrakis (piperidinocarbonylmethoxy) calix [4] arene (5), 5,11,17,23,29,35,41,47-octa-t-butyl-49,50,51,52,53,54,55,56-octa (piperidinocarbonylmethoxy) calix[8]arene (6) and 5,11,17,23,29,35,41,47-octa-t-butyl-49,50,51,52,53,54,55,56-octa(N,N-diethylcarbamoylmethoxy) calix[8]arene (7). The UV spectra of 6 and 7 revealed they had an ability to transform tight lead picrate ion pairs into separated ones by complexation with Pb2+ in tetrahydrofuran. Both derivatives give 1: 1 complexes with Pb2+. Extraction studies showed that these derivatives could efficiently extract Pb2+ (as picrate salts) from the aqueous phase into chloroform. The extractability of these derivatives were also compared with that of the oxygen-containing ester derivative calix [8] arene 2 and the other two nitrogen-containing compounds 8 and 9.

The molecular recognition of tetra (p-t-butyl) tetrathiocalix [4] arene (I) and its three derivatives to heavy metal ions has been investigated by UV spectroscopy and solvent extraction. These erivatives include 5, 11, 17, 23,-tetra-t-butyl-25, 26, 27, 28-tetrakis (acetylmethoxy) tetrathiocalix [4] arene (II), 5, 11, 17,23-tetra-t-butyl-25, 26, 27, 28-tetrakis (2'-hydroxypropyloxy) tetrathiocalix [4] arene (III), 5, 11, 17, 23,-tetra-t-butyl-25, 27-bis (3'-hydroxy propyloxy) tetrathiocalix [4] arene (IV). The UV spectra and solvent extraction of I show that it has an effective molecular recognition to heavy metal ions, especially to Cd2, while IV has a special molecular recognition to Agion. These results confirmed the feasibilities for I to be applied in separation for toxic heavy metal ions Pb2, Cd2 and IV to be used as the sensor compound of Ag ion-selective electrode.

The tetranjuo denivative 3 of thiacalix [4] arene was synthesixed and characterixed. Its aciel-hase water solution were studied by UV spectroscopy. The four pKa walues of 3 were determined by target testi analysis (TTFA). The pure UVabsorqton curves and pH distribution curves of five fornes of 3 presented solution were also caculatied by TTFA.

The tetraamino derivative of thiacalix [4] arene (4) was synthesized and characterized. Its acid-base property in water solution was studied by UV spectroscopy. The pH distribution regions of several acidic or basic species of 4 were determined.

Three new thiacalix [4] arene derivatives, 5,11,17,23-tetra-tert-butyl-25,27-di (2-hydroxyethoxy)-26,28-dihydroxythiacalix-[4] arene (2), 5,11,17,23-tetra-tert-25, 26,27,28-tetrakis [(methylcarboxyl)methoxy] thiacalix [4] arene (3), 5,11,17,23-tetratert-butyl-25,26,27,28-tetrakis(2-hydroxy-1-propanoxy)thiacalix [4] arene (4), were synthesized for the first time. The coordination properties of thiacalix [4] arene (1) and its derivatives (2and4) were investigated by detecting the interactions between these compounds and two palladium complexes, cis-[Pd(en)(H2O)2]2+ and cis-[Pd(dtco-3-OH)(H2O)2]2+, by means of electrospray ionization mass spectrometry (ESI-MS) technique.