Novel Supramolecular fluorescence receptor derived from calix-system i.e. calix[4]resorcinarene bearing dansylchloride as fluorophore was designed and synthesized. The compound was purified by column chromatography and characterized by elemental analysis, NMR and Mass spectroscopy. Tetradansylated calix[4] resorcinarene (TDCR) shows a boat conformation with C(2)v symmetry. The complexation behaviour of metal cations [Ag(I), Cd(II), Co(II), Fe(III), Hg(II), Cu(II), Pb(II), Zn(II), U(VI) (1 × 10(-4) M)] with tetra dansylated calix[4]resorcinarene (1 × 10(-6) M) was studied by spectophotometry and spectrofluorometry. Red shift in the absorption spectra led us to conclude that there is strong complexation Fe(III), Co(II) and Cu(II) with TDCR. These metal cations also produce quenching with red shifts in the emission spectra. The maximum quenching in emission intensity was observed in the case of Fe(III) and its binding constant was also found to be significantly higher than that of Co(II) and Cu(II). Quantum yield of metal complexes of Fe(III) was found to be lower in comparison with Co(II) and Cu(II) complexes. Stern Volmer analysis indicates that the mechanism of fluorescence quenching is either purely dynamic, or purely static.
A new octa functionalized calix[4]resorcinarene bearing eight hydroxamic acid groups (OFCHA) has been synthesized and its analytical properties have been investigated. To elucidate the structure of the compound, elemental analysis, FT-IR and 1 H NMR spectral data have been used. The compound showed high affinity and selectivity for vanadium(V) in presence of large quantities of associated metal ions. The complexation of vanadium(V) with OFCHA has a 4:1 metal: ligand stoichiometry as evaluated by Job's plot. A spectrophotometric method is proposed for the extractive determination of vanadium(V) in an acidic medium in the presence of diversified matrix, and verified by ICP-AES. Under the optimum condition of acidity, solvent, interfering ions and OFCHA concentration, the molar absorptivity of the complex is 5630 l mol -1 cm -1 at 495 nm. The system obeys Beer's law over the range 0.125-8.75 μg ml -1 of vanadium(V) with Sandell sensitivity 0.009 μg cm -2 . The preconcentration factor and overall stability constant evaluated at 25 qC were 142 and 14.18, respectively. The complexation is characterized by favorable enthalpy and entropy changes. Liquid membrane transport studies of vanadium(V) were carried out from source to the receiving phase under controlled conditions and a mechanism for transport is suggested. To check the validity of the proposed method, vanadium is determined in environmental, biological samples and some standard reference materials from NIST and BCS.
In the present study, we report the synthesis of aqueous stable gold nanoparticles by using calix[4]arene polyhydrazide (CPH) as both reducing and capping agents. The calix[4]arene polyhydrazide reduced gold nanoparticles (CPH-AuNps) were characterized by UV/Vis, particle size analyzer (PSA) and transmission electron mictroscopy (TEM). The records confirmed high stability of CPH-AuNps in aqueous solution over a long period of time and even at varied pH. Additionally, CPH-AuNps have been investigated for its application as "Turn Off" fluorescent sensor for Hg[II]. A concentration of Hg[II] in the limit of 10 nM to 10 microM can be detected based on fluorescence quenching of the CPH-AuNPs and it was also concluded from the spectroscopic data that CPH-AuNPs possess excellent selectivity to Hg[II] over several metal ions like Pb[II], Cu[II], Cd[II], Mn[II], Zn[II] and Ni[II].
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