Colorimetric detection of Fe3+ ions using pyrophosphate functionalized gold nanoparticles.

A sensitive, selective colorimetric Fe(3+) detection method has been developed by using pyrophosphate functionalized gold nanoparticles (P(2)O(7)(4-)-AuNPs). Gold nanoparticles were prepared by reducing HAuCl(4) with sodium borohydride, in the presence of Na(4)P(2)O(7). IR spectra suggested that pyrophosphates were capped on the surface of the gold nanoparticles. Aggregation of P(2)O(7)(4-)-AuNPs was induced immediately in the presence of Fe(3+) ions, yielding a color change from pink to violet. This Fe(3+)-induced aggregation of P(2)O(7)(4-)-AuNPs was monitored using first the naked eye and then UV-vis spectroscopy with a detection limit of 5.6 µM. The P(2)O(7)(4-)-AuNPs bound by Fe(3+) showed excellent selectivity compared to other metal ions (Ca(2+), Cd(2+), Co(2+), Fe(2+), Hg(2+), K(+), Mg(2+), Mn(2+), Na(+), Ni(2+), Pb(2+), and Zn(2+)). The best detection of Fe(3+) was achieved in a pH range from 3 to 9. In addition, the P(2)O(7)(4-)-AuNPs were also used to detect Fe(3+) in lake water samples, with low interference.

An NAD(P)H:quinone oxidoreductase 1 (NQO1) enzyme responsive nanocarrier based on mesoporous silica nanoparticles for tumor targeted drug delivery in vitro and in vivo.

The synthesis and characterization of an NAD(P)H: quinone oxidoreductase 1 (NQO1) enzyme responsive nanocarrier based on mesoporous silica nanoparticles (MSNPs) for on-command delivery applications has been described in this paper. Gatekeeping of MSNPs is achieved by the integration of mechanically interlocked rotaxane nanovalves on the surface of MSNPs. The rotaxane nanovalve system is composed of a linear stalk anchoring on the surface of MSNPs, an α-cyclodextrin ring that encircles it and locks the payload "cargo" molecules in the mesopores, and a benzoquinone stopper incorporated at the end of the stalk. The gate opening and controlled release of the cargo are triggered by cleavage of the benzoquinone stopper using an endogenous NQO1 enzyme. In addition to having efficient drug loading and controlled release mechanisms, this smart biocompatible carrier system showed obvious uptake and consequent release of the drug in tumor cells, could selectively induce the tumor cell death and enhance the capability of inhibition of tumor growth in vivo. The controlled drug delivery system demonstrated its use as a potential theranostic material.

Quinone-Modified Mn-Doped ZnS Quantum Dots for Room-Temperature Phosphorescence Sensing of Human Cancer Cells That Overexpress NQO1.

Early detection of cancer cells in a rapid and sensitive approach is one of the great challenges in modern clinical cancer care. This study has demonstrated the first example of a rapid, selective, and sensitive phosphorescence probe based on phosphorescence energy transfer (PET) for cancer-associated human NAD(P)H: quinone oxidoreductase isozyme 1 (NQO1). An efficient room-temperature phosphorescence NQO1 probe was constructed by using Mn-doped ZnS quantum dots (Mn:ZnS QDs) as donors and trimethylquinone propionic acids as acceptors. Phosphorescence quenching of Mn:ZnS QDs from the Mn:ZnS QDs to a covalently bonded quinone was achieved through PET. Phosphorescence of Mn:ZnS QDs was turned on by the rapid reduction-initiated removal of the quinone quencher by NQO1. This probe shows low cellular toxicity and can rapidly distinguish between NQO1-expressing and -nonexpressing cancer cell lines through phosphorescence imaging.

The oxidation of phenylhydrazine by tyrosinase.

Tyrosinase was found to catalyze the oxidation of phenylhydrazine to phenol in a reaction that did not resemble those typically performed by tyrosinase. The kinetics of this reaction was investigated by measuring the initial velocity of the formation of phenol (25 °C). The values of k cat and K M for the oxidation of phenylhydrazine were obtained as 11.0 s(-1) and 0.30 mM, respectively. The generation of superoxides during the oxidation of phenylhydrazine by tyrosinase was monitored by nitroblue tetrazolium (NBT) assay. In the phenylhydrazine-tyrosinase reaction, 1 mol O2 was required for the production of 1 mol phenol and 1/6 mol superoxide. The decomposition of superoxide by superoxide dismutase enhanced the rate constant of the oxidation of phenylhydrazine. Phenol formed in the oxidation of phenylhydrazine by tyrosinase was further oxidized by tyrosinase to an o-quinone, after the oxidation of phenylhydrazine by tyrosinase was almost completed.

Colorimetric detection of Al3+ ions using triazole-ether functionalized gold nanoparticles.

A sensitive, selective colorimetric Al(3+) detection method has been developed by using triazole-ether functionalized gold nanoparticles (TTP-AuNPs). Gold nanoparticles were prepared by reducing HAuCl4 with sodium borohydride in the presence of 5-(1,2-dithiolan-3-yl)-N-(prop-2-yn-1-yl)pentanamide (TP). The azide part of 2-[2-(2-azidoethoxy)ethoxy]ethanol and the acetylene part of TP were combined to form a triazole structure through a click reaction. Aggregation of TTP-AuNPs was induced immediately in the presence of Al(3+) ions, yielding a color change from red to blue. This Al(3+)-induced aggregation of TTP-AuNPs was monitored first with the naked eye and then UV-vis spectroscopy with a detection limit of 18.0 nM. The TTP-AuNPs showed excellent selectivity for Al(3+), compared to other metal ions (Ag(+), Ca(2+), Cd(2+), Co(2+), Cu(2+), Cr(3+), Fe(2+), Fe(3+), Hg(2+), Mg(2+), Mn(2+), Ni(2+), Pb(2+), and Zn(2+)). In addition, TTP-AuNPs were used to detect Al(3+) in sea water samples, with low interference.

Colorimetric sensing of Cu(II): Cu(II) induced deprotonation of an amide responsible for color changes.

9,10-Anthraquinone-based chemosensor 1 indicates the presence of Cu(II) ions among other transition metal ions with high selectivity by a color change from yellow to dark red. Chemosensor 2 shows binding toward Cu(II), Ni(II) and Co(II) with color changes from yellow to dark red, red and pale green, respectively. Especially, Co(II) binding with chemosensor 2 causes significantly green fluorescence. On addition of Cu(II), 1 and 2 exhibit 76 and 80 nm red shifts in absorption wavelength (pH 7.0). The effect on pH by the formation of these 1-Cu(II) and 2-Cu(II) complexes was determined by UV-vis spectroscopic pH titration. In the pH range of 6-7.5, a maximum absorption was observed at 473 nm and exhibited the formation of deprotonated 1-Cu(II) and 2-Cu(II) complexes.