Synthesis of pyrazolylbisindoles over mesoporous Lewis acidic ZrTUD-1: Potential application in selective Cu(2+) colorimetric detection.

A series of pyrazolylbisindole (PBI) derivatives were prepared by simple condensation of indole and pyrazole aldehyde utilizing amorphous mesoporous ZrTUD-1 having predominant Lewis acid sites. The applicability of pyrazolylbisindolyl derivate as a colorimetric chemosensor with high selectivity toward Cu(2+) over other cations were tested. Among heavy and transition metal (HTM) ions in CH3CN solution, the probe only sensed Cu(2+) detectable by naked eye. The sensor exhibited a new absorption band at 488 nm (a red shift of 206 nm from 282 nm) with a large colorimetric response and affinity to Cu(2+) over other cations tested (Al(3+), Pb(2+), Cd(2+), Mg(2+), Mn(2+), Zn(2+), K(+), Fe(2+), Ca(2+), Cu(2+) and Hg(2+)).

On the synergistic catalytic properties of bimetallic mesoporous materials containing aluminum and zirconium: the Prins cyclisation of citronellal.

Bimetallic three-dimensional amorphous mesoporous materials, Al-Zr-TUD-1 materials, were synthesised by using a surfactant-free, one-pot procedure employing triethanolamine (TEA) as a complexing reagent. The amount of aluminium and zirconium was varied in order to study the effect of these metals on the Brønsted and Lewis acidity, as well as on the resulting catalytic activity of the material. The materials were characterised by various techniques, including elemental analysis, X-ray diffraction, high-resolution TEM, N(2) physisorption, temperature-programmed desorption (TPD) of NH(3), and (27) Al MAS NMR, XPS and FT-IR spectroscopy using pyridine and CO as probe molecules. Al-Zr-TUD-1 materials are mesoporous with surface areas ranging from 700-900 m(2) g(-1), an average pore size of around 4 nm and a pore volume of around 0.70 cm(3) g(-1). The synthesised Al-Zr-TUD-1 materials were tested as catalyst materials in the Lewis acid catalysed Meerwein-Ponndorf-Verley reduction of 4-tert-butylcyclohexanone, the intermolecular Prins synthesis of nopol and in the intramolecular Prins cyclisation of citronellal. Although Al-Zr-TUD-1 catalysts possess a lower amount of acid sites than their monometallic counterparts, according to TPD of NH(3), these materials outperformed those of the monometallic Al-TUD-1 as well as Zr-TUD-1 in the Prins cyclisation of citronellal. This proves the existence of synergistic properties of Al-Zr-TUD-1. Due to the intramolecular nature of the Prins cyclisation of citronellal, the hydrophilic surface of the catalyst as well as the presence of both Brønsted and Lewis acid sites synergy could be obtained with bimetallic Al-Zr-TUD-1. Besides spectroscopic investigation of the active sites of the catalyst material a thorough testing of the catalyst in different types of reactions is crucial in identifying its specific active sites.

Synergy between Brønsted acid sites and Lewis acid sites.

Synergy between Brønsted acid sites and Lewis acid sites in mesoporous Al-Zr-TUD-1 was demonstrated to exist in Brønsted acid catalysed reactions, but not in Lewis acid catalysed reactions.