A luminescence-based probe for sensitive detection of hydrogen peroxide in seconds

Here, we present a fast and simple hydrogen peroxide assay that is based on time-resolved fluorescence. The emission intensity of a complex consisting of terbium ions (Tb³⁺) and phthalic acid (PA) in HEPES buffer is quenched in the presence of H₂O₂ and this quenching is concentration-dependent. The novel PATb assay detects hydrogen peroxide at a pH range from 7.5 to 8.5 and with a detection limit of 150 nmol L⁻¹ at pH 8.5. The total assay time is less than 1 min. The linear range of the assay can be adapted by a pH adjustment of the aqueous buffer and covers a concentration range from 310 nmol L⁻¹ to 2.56 mmol L⁻¹ in total which encompasses four orders of magnitude. The assay is compatible with high concentrations of all 47 tested inorganic and organic compounds. The PATb assay was applied to quantify H₂O₂ in polluted river water samples. In conclusion, this fast and easy-to-use assay detects H₂O₂ with high sensitivity and precision.     

High-speed peak matching algorithm for retention time alignment of gas chromatographic data for chemometric analysis

A rapid retention time alignment algorithm was developed as a preprocessing utility to be used prior to chemometric analysis of large datasets of diesel fuel profiles obtained using gas chromatography (GC). Retention time variation from chromatogram-to-chromatogram has been a significant impediment against the use of chemometric techniques in the analysis of chromatographic data due to the inability of current chemometric techniques to correctly model information that shifts from variable to variable within a dataset. The alignment algorithm developed is shown to increase the efficacy of pattern recognition methods applied to diesel fuel chromatograms by retaining chemical selectivity while reducing chromatogram-to-chromatogram retention time variations and to do so on a time scale that makes analysis of large sets of chromatographic data practical. Two sets of diesel fuel gas chromatograms were studied using the novel alignment algorithm followed by principal component analysis (PCA). In the first study, retention times for corresponding chromatographic peaks in 60 chromatograms varied by as much as 300 ms between chromatograms before alignment. In the second study of 42 chromatograms, the retention time shifting exhibited was on the order of 10 s between corresponding chromatographic peaks, and required a coarse retention time correction prior to alignment with the algorithm. In both cases, an increase in retention time precision afforded by the algorithm was clearly visible in plots of overlaid chromatograms before and then after applying the retention time alignment algorithm. Using the alignment algorithm, the standard deviation for corresponding peak retention times following alignment was 17 ms throughout a given chromatogram, corresponding to a relative standard deviation of 0.003% at an average retention time of 8 min. This level of retention time precision is a 5-fold improvement over the retention time precision initially provided by a state-of-the-art GC instrument equipped with electronic pressure control and was critical to the performance of the chemometric analysis. This increase in retention time precision does not come at the expense of chemical selectivity, since the PCA results suggest that essentially all of the chemical selectivity is preserved. Cluster resolution between dissimilar groups of diesel fuel chromatograms in a two-dimensional scores space generated with PCA is shown to substantially increase after alignment. The alignment method is robust against missing or extra peaks relative to a target chromatogram used in the alignment, and operates at high speed, requiring roughly 1 s of computation time per GC chromatogram.     

Ba6(MN4)N2–x (M = MoVI/TaV), a Subvalent Nitridometalate with Perovskite‐like Crystal Structure

The subvalent nitridometalate Ba₆[(Mo_1–xTa_x)N₄]N_0.86 was prepared from mixtures of Mo powder with Ba, Na, and Ba₂N at 600 °C in Ta ampoules. It crystallizes in space group Cmcm with a = 11.672(3), b = 10.177(2) and c = 10.8729(19) Å. Its crystal structure exhibits an orthorhombically distorted Perovskite topology with [Ba₆N] building units forming the ReO₃‐type lattice via common vertices, and the nitridometalate anions occupying half of the available distorted cuboctahedral interstices. [MN₄] anions show statistically mixed occupancy of M by Mo^VI and Ta^V. They show no notable deviation from nitridometalate anions in known ionic nitridomolybdates and ‐tantalates, and the metrics of the [Ba₆N] octahedra correspond to those found in similar subvalent compounds. The nitrogen atom position centering the [Ba₆N] octahedra is underoccupied. Band structure calculations corroborate the subvalent character of the compound and the two individual anionic structural building units.     

Zur Charakterisierung von Eigenschaften der versteiften dreizähnigen Aminophosphanliganden N,N'-Bis(diphenylphosphino)-2,6-diaminopyridin und N,N-Bis(diphenylphosphino)-2-aminopyridin mit Metallen der Chromgruppe

Inhaltsübersicht. Edukte von Typ M(CO)₆ (M = Cr, Mo,W), N,N'-Bis(diphenylphosphino)-2,6-diaminopyridin (PNP) und Trimethylaminoxid setzen sich bei Raumtemperatur nicht zu dem bekannten Verbindungstyp mer-M(CO)₃PNP, sondern zu Verbindungen der beiden Typen M(CO)₄(PNP=O) mit zweizähnig koordinierten Liganden PNP=O und M(CO)₅(NMe₃) um. Die zu Vergleichszwecken untersuchte Oxidation eines koordinierten PNP-Liganden von mer-Mo(CO)₃(PNP) in Tetramethylbenzollösung ergibt mit Luftsauerstoff bei 180°C eine Reaktion unter Spaltung der P–N-Bindung zur cubanartigen Verbindung Mo₄(μ₃-O)₄(μ-Ph₂PO₂)₄O₄ (Ausbeute 48%). In einem Glaseinschlußrohr reagiert der ambidente N,N-Bis(diphenyIphosphino)-2-nminopyridin-Ligand (NPP) mit den Hexacarbonylen M(CO)₆ in Toluollösung bei 140°C zu Verbindungen des Typs M(CO)₄(NPP) mit zweizähniger Verknüpfung des NPP-Liganden. Hierbei bilden die beiden P-Donoratome am Aminstickstoffatom einen MP₂N-Chelatvierring an Stelle des ebenfalls möglichen P, N_py-Chelatfünfrings. Der analoge Chelatvierring entsteht gleichfalls bei einer Ligandensubstitutions-reaktion zwischen Verbindungen des Zweikernkomplextyps MM′(CO)₈(μ-PPh₂)₂ (M = M′ = W; M = Mo, M′ = W) bzw. \V(CO)₄(μ-PPh₂)₂IrH(CO)(PPh₃) und NPP. Er bildet sich außerdem bei der Thermolyse von Mo(CO)₄(NPP) zu Mo₂(CO)₆(μ-PPh₂)₂(NPP). Die Identifizierung erfolgt im Falle der Verbindungen Mo(CO)₄(PNP=O), Mo₄(μ₃-O)₄(μ-Ph₂PO₂)₄O_4′ Mo₂(CO)₆(μ-PPh₂)₂(NPP) und W(CO)₄(μ-PPh₂)₂IrH(CO)(NPP) durch Einkristall-Röntgenstrukturanalysen. Alle isolierten Produkte werden durch spektroskopische Messungen insbesondere ³¹P-NMR-Daten charakterisiert. Characterization of Properties of the Rigid Tridentate Chelate Ligand N,N′-Bis(diphenylphosphino)-2,6-diaminopyridine and N,N-Bis(diphenylphosphino)-2-aminopyridine with Transition Metals of the Chromium Group Hexacarbonyls M(CO)₆ (M = Cr, Mo, W), N,N′-Bis(diphenylphosphino)-2,6-diaminopyridine (PNP) and trimethylamine oxide gave products of two types M(CO)₄(PNP=O) having a bidentate ligand PNP=O and M(CO)₅(NMe₃) instead of the desired mer-M(CO)₃PNP. For the purpose of a comparison, aerial oxidation of mer-Mo(CO)₃PNP in tetramethyl benzene solution at 180°C was examined which resulted a P–N bond rupture under formation of the cubane-like product Mo₄(μ₃-O)₄(μ-Ph₂PO₂C₄O₄){yield 48%). In sealed glass tubes the ambidentate ligand N,N-bis(diphenylphosphino)-2-aminopyridine (NPP) was reacted with the hexacarbonyls M(CO)₆ in toluene solution at 140°C to products of the type M(CO)₄NPP with NPP as bidentate ligand. Under this reaction conditions the four-membered chelate ring of the type MP₂N was formed with the two P donor atoms attached to the amine N atom instead of the possible competitive five-membered chelate ring formation with a P and pyridyl nitrogen. The analogous four-membered chelate ring was formed in ligand substitution reactions between the substance NPP and each of the dinuclear coordination compounds MM′(CO)₈(μ-PPh₂)₂ (M = M′ = W, M = Mo, M′ = W) including W(CO)₄(μ-PPh₂)₂IrH(CO)(PPh₃); Mo₂(CO)6(μ-PPh₂)₂(NPP) was obtained via thermolysis of Mo(CO)₄(PNP=O). The given structural identification of the compounds Mo(CO)₄(PNP=O), Mo₄(μ₃-O)₄(μ-Ph₂PO₂)₄O₄, Mo₂(CO)₆ (μ-PPh₂)₂(NPP) and W(CO)₄(μ-PPh₂)₂IrH(CO) (NPP) was done by single-crystal X-ray analysis. All seperated products have been characterized by means of spectroscopic measurements especially ³¹P n.m.r. data.     

Chemo-genetic optimization of DNA recognition by metallodrugs using a presenter-protein strategy

The mode of action of precious metal anticancer metallodrugs is generally believed to involve DNA as a target. However, the poor specificity of such drugs often requires high doses and leads to undesirable side-effects. With the aim of improving the specificity of a ruthenium piano-stool complex towards DNA, we employed a presenter protein strategy based on the biotin-avidin technology. Guided by the X-ray structure of the assembly of streptavidin and a biotinylated piano-stool, we explored the formation of metallodrug-mediated ternary complexes with the presenter protein and DNA. The assemblies bound more strongly to telomere G-quadruplexes than to double-stranded DNA; chemo-genetic modifications (varying the complex or mutating the protein) modulated binding to these targets. We suggest that rational targeting of small molecules by presenter proteins could be exploited to bind metallodrugs to preferred macromolecular targets.     

Correlation between the fluorescent response of microfluidity probes and the water content and viscosity of ionic liquid and water mixtures

Accurate data on transport properties such as viscosity are essential in plant and process design involving ionic liquids. In this study, we determined the absolute viscosity of the ionic liquid + water system at water mole fractions from 0 to 0.25 for three 1-alkyl-3-methylimidazolium ionic liquids: 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide and 1-ethyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide. In each case, the excimer to monomer ratio for 1,m-bis(1-pyrenyl)alkanes (m= 3 or 10) was found to increase linearly with the mole fraction of water. Of the probes studied only PRODAN and rhodamine 6G, both of which have the ability to participate in hydrogen bonding, exhibited Perrin hydrodynamic behavior in the lower viscosity bis(trifluoromethane sulfonyl)imides. As a result, these probes allow for the extrapolation of the absolute viscosity of the ionic liquid mixture from the experimental fluorescence steady-state polarization values.     

Fluoride-facilitated deuterium exchange from DMSO-d6 to polyamide-based cryptands

Multiple deuterium exchange between DMSO-d6 and amide hydrogens in two hexaamido cryptand fluoride receptors has been verified by 19F and 2H NMR and FAB mass spectral studies. Structural results for one of the complexes indicate a tricapped trigonal prism hydrogen bond coordination geometry around an encapsulated fluoride, with hydrogen bonds from fluoride to six amide and three phenyl hydrogens.