Colorimetric Probe for Mn2+ Using a Mixture of an Anionic Dye and a Cationic Polyelectrolyte in an Aqueous Solution.

A novel colorimetric probe for Mn2+ was easily prepared by mixing negatively charged alizarin complexone (ALC) with positively charged poly[bis(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl]urea] (PQ-2) in aqueous solutions at pH 6.0. Upon adding Mn2+ to ALC alone, the solution underwent no distinct color change, while the mixture displayed selective detection of Mn2+ over different physiological and environmentally significant metal ions by an efficient naked-eye color change from red to purple. The detection of Mn2+ by the mixture was achieved from the electrostatic interactions between ALC and PQ-2. The quantitative determination of Mn2+ was obtained by spectrophotometric measurement and naked-eye observation. This sensing strategy can be an attractive approach for the development of new colorimetric probes due to the advantages such as no organic synthesis, facile fabrication, and simple visual detection.

Colorimetric Detection of ATP by a Chlorophosphonazo III -based Mg2+ Complex in Aqueous Solution via Indicator Displacement Approach.

A simple and effective colorimetric detection of adenosine 5-triphosphate (ATP) in 100% aqueous media was developed based on an indicator displacement approach (IDA). A commercially available dye, Chlorophosphonazo III (CPA), was utilized as the indicator and the ATP detection was achieved using the complex of CPA with Mg2+ in a 2:1 stoichiometric ratio (CPA2-Mg2+) through the regeneration of CPA by the binding of ATP to Mg2+. Upon addition of a series of anions to the CPA2-Mg2+ complex, only the appearance of the solution of the complex with ATP exhibited a color change from blue to purple which can be detected by the naked eye. Moreover, the ATP recognition was not hampered by the presence of other anions. Hence, CPA2-Mg2+ is efficient in ATP highly selective and sensitive colorimetric detection in 100% aqueous media.

4-O-Glucosylation of Trichothecenes by Fusarium Species: A Phase II Xenobiotic Metabolism for t-Type Trichothecene Producers.

The t-type trichothecene producers Fusarium sporotrichioides and Fusarium graminearum protect themselves against their own mycotoxins by acetylating the C-3 hydroxy group with Tri101p acetylase. To understand the mechanism by which they deal with exogenously added d-type trichothecenes, the Δtri5 mutants expressing all but the first trichothecene pathway enzymes were fed with trichodermol (TDmol), trichothecolone (TCC), 8-deoxytrichothecin, and trichothecin. LC-MS/MS and NMR analyses showed that these C-3 unoxygenated trichothecenes were conjugated with glucose at C-4 by α-glucosidic linkage. As t-type trichothecenes are readily incorporated into the biosynthetic pathway following the C-3 acetylation, the mycotoxins were fed to the ΔFgtri5ΔFgtri101 mutant to examine their fate. LC-MS/MS and NMR analyses demonstrated that the mutant conjugated glucose at C-4 of HT-2 toxin (HT-2) by α-glucosidic linkage, while the ΔFgtri5 mutant metabolized HT-2 to 3-acetyl HT-2 toxin and T-2 toxin. The 4-O-glucosylation of exogenously added t-type trichothecenes appears to be a general response of the ΔFgtri5ΔFgtri101 mutant, as nivalenol and its acetylated derivatives appeared to be conjugated with hexose to some extent. The toxicities of 4-O-glucosides of TDmol, TCC, and HT-2 were much weaker than their corresponding aglycons, suggesting that 4-O-glucosylation serves as a phase II xenobiotic metabolism for t-type trichothecene producers.

Colorimetric detection of homocysteine by a pyridylazo dye-based Cu2+ complex via indicator displacement mechanism.

A BrPAPS based Cu2+ complex has been developed as a colorimetric probe for the selective recognition of homocysteine (Hcy) over cysteine (Cys) and glutathione (GSH) in an aqueous solution via the indicator displacement assay. BrPAPS formed a complex with Cu2+ in a 1:1 ratio (BrPAPS-Cu2+) accompanied by the color change from yellow to red. Detecting Hcy is based on high affinity of Hcy for Cu2+. The addition of Hcy to BrPAPS-Cu2+ caused the complex formation of Hcy with Cu2+ in a 2:1 stoichiometry, resulting a hypsochromic shift with change back of color from red to yellow by the release of BrPAPS from BrPAPS-Cu2+. The absorption response is linear with the Hcy concentration in the range of 0-20 µM with a detection limit of 1.46 µM. Moreover, the detection of Hcy was not significantly affected by other amino acids from the competition experiments. Thus, BrPAPS-Cu2+ can be used as a simple probe for Hcy in aqueous solution.

Colorimetric Chemosensor for Hg2+ Based on Nuclear Fast Red and a Cationic Polyelectrolyte in Aqueous Solution.

We have developed a colorimetric chemosensor based on an anionic organic dye, commercially available nuclear fast red (NFR) and a cationic polyelectrolyte, poly(diallyldimethylammonium chloride) (PDADMAC) for detection of Hg2+ in aqueous solution at physiological conditions. Upon addition of Hg2+, a bathchromic shift in the absorption was observed concomitantly with color change from pink to reddish violet which was easily detectable by the naked eye, while such a change was not observed for NFR alone, indicating that PDADMAC played an important role in detecting Hg2+. This investigation can propose the simple and valuable construction method for a novel chemosensor by mixture of a water-soluble organic dye and an oppositely charged polyelectrolyte.

Reduced Toxicity of Trichothecenes, Isotrichodermol, and Deoxynivalenol, by Transgenic Expression of the Tri101 3-O-Acetyltransferase Gene in Cultured Mammalian FM3A Cells.

In trichothecene-producing fusaria, isotrichodermol (ITDol) is the first intermediate with a trichothecene skeleton. In the biosynthetic pathway of trichothecene, a 3-O-acetyltransferase, encoded by Tri101, acetylates ITDol to a less-toxic intermediate, isotrichodermin (ITD). Although trichothecene resistance has been conferred to microbes and plants transformed with Tri101, there are no reports of resistance in cultured mammalian cells. In this study, we found that a 3-O-acetyl group of trichothecenes is liable to hydrolysis by esterases in fetal bovine serum and FM3A cells. We transfected the cells with Tri101 under the control of the MMTV-LTR promoter and obtained a cell line G3 with the highest level of C-3 acetylase activity. While the wild-type FM3A cells hardly grew in the medium containing 0.40 µM ITDol, many G3 cells survived at this concentration. The IC50 values of ITDol and ITD in G3 cells were 1.0 and 9.6 µM, respectively, which were higher than the values of 0.23 and 3.0 µM in the wild-type FM3A cells. A similar, but more modest, tendency was observed in deoxynivalenol and 3-acetyldeoxynivalenol. Our findings indicate that the expression of Tri101 conferred trichothecene resistance in cultured mammalian cells.

Exploring an Artificial Metabolic Route in Fusarium sporotrichioides: Production and Characterization of 7-Hydroxy T-2 Toxin.

An artificial metabolic route to an unnatural trichothecene was designed by taking advantage of the broad substrate specificities of the T-2 toxin biosynthetic enzymes of Fusarium sporotrichioides. By feeding 7-hydroxyisotrichodermin, a shunt pathway metabolite of F. graminearum, to a trichodiene synthase-deficient mutant of F. sporotrichioides, 7-hydroxy T-2 toxin (1) was obtained as the final metabolite. Such an approach may have future applications in the metabolic engineering of a variety of fungal secondary metabolites. The toxicity of 7-hydroxy T-2 toxin was 10 times lower than that of T-2 toxin in HL-60 cells.

Colorimetric detection of oxalate in aqueous solution by a pyrogallol red-based Cu2+ complex.

The pyrogallol red (PR)-based Cu2+ complex was proven to be an effective and selective colorimetric chemosensing ensemble for recognition of oxalate over other anions in a perfect aqueous solution. The addition of oxalate to the PR-Cu2+ complex resulted in a colour change from purple to orange colour due to the regeneration of PR by the chelation of oxalate with Cu2+ , while other anions did not induce any significant colour change. Moreover, it was revealed that no obvious interference was observed during the titrations with oxalate into each other anion. Therefore, the PR-Cu2+ complex can be used as a simple and practical colorimetric chemosensor for detecting oxalate.

Colorimetric Determination of Pb2+ in Perfect Aqueous Solution Using Carminic Acid as a Selective Chemosensor.

The commercially available natural organic dye, carminic acid (CA), an anthraquinone derivative bearing hydroxyl and carboxyl groups as recognition sites was found to be a colorimetric probe for Pb2+ in perfect aqueous solution under neutral conditions with specific selectivity and high sensitivity. Upon addition of Pb2+, the absorption maximum of CA showed a large red shift, and the resulted color change from red to purple could be easily identified even by the naked eye. The chemical stoichiometric ratio between CA and Pb2+ was determined to be 1:2 through Job plot, Pb2+ titration, and kinetic experiments. Moreover, other environmental relevant metal ions induced no or minimal spectral and color changes. The reversibility of Pb2+ to CA with EDTA even through several cycles was established for practical applications. The results indicated that CA can be a good candidate for simple, convenient and reversible colorimetric detection of Pb2+ in aqueous solution even though it was hard to be applied to determine Pb2+ on the water testing by US EPA.