Experimental and theoretical study on the absorption and fluorescence properties of substituted aryl hydrazones of 1,8-naphthalimide

Absorption and fluorescence spectra in acetonitrile for a series of substituted aryl hydrazones of N-hexyl-1,8-naphthalimide are studied with the aim of potential application of the compounds for enzyme activity localization. The influence of the substituents on the spectral characteristics has been evaluated. The absorption and fluorescence energies of substituted aryl-1,8-naphthalimide hydrazones have been calculated with the PCM TDDFT formalism. The M06 and PBE0 functionals, combined with the 6-31+G(d) atomic basis set, have been found to accurately model the excited state properties of the present set of solvated fluorophores. Absorption and fluorescence spectral characteristics have been rationalized in terms of experimental and theoretical electronic indices in order to assess their predictive abilities for application in designing analogues with good emitting properties. An excellent linear dependence is established between the experimental fluorescence and Hammett σ(p)(+) substituent constants and on the other hand σ(p)(+) constants correlate with the theoretically calculated values for the electrostatic potential at nuclei (EPN). A model for predicting the fluorescence properties of substituted hydrazones by means of EPN is drawn, including the polysubstituted derivatives, where Hammett constants are not applicable.     

The utility of ultra-performance liquid chromatography/electrospray ionisation time-of-flight mass spectrometry for multi-residue determination of pesticides in strawberry

The utility of ultra-performance liquid chromatography/orthogonal-acceleration time-of flight mass spectrometry (UPLC/TOFMS) for the rapid qualitative and quantitative analysis of 100 pesticides targeted in strawberry was assessed by comparing results with those obtained using a validated in-house UPLC tandem mass spectrometry (MS/MS) multi-residue method. Crude extracts from retail strawberry samples received as part of the 2007 annual UK pesticide residues in food surveillance programme were screened for the presence of pesticide residues using UPLC/TOFMS. Accurate mass measurement of positive and negative ions allowed their extraction following 'full mass range data acquisition' with negligible interference from background or co-eluting species observed during UPLC gradient separation (in a cycle time of just 6.5 min per run). Extracted ion data was used to construct calibration curves and to detect and identify any incurred residues (i.e. pesticides incorporated in or on the test material following application during cultivation, harvest and storage). Calibration using matrix-matched standards was performed over a narrow concentration range of 0.005-0.04 mg kg(-1) with determination coefficients (r2) > or =0.99 for all analytes with the exception of malathion/fenarimol/fludioxanil (r2 = 0.98), quassia/pymetrazine (r2 = 0.97) and fenthion sulfone (r2 = 0.95). Residues found in selected samples ranged from 0.025-0.28 mg kg(-1) and were in excellent agreement with results obtained using UPLC/MS/MS. Mass measurement accuracies of < or =5 ppm were achieved consistently throughout the separation, mass range and concentration range of interest thus providing the opportunity to obtain discrete elemental compositions of target ions.     

Mechanism of the glutathione transferase-catalyzed conversion of antitumor 2-crotonyloxymethyl-2-cycloalkenones to GSH adducts

Human glutathione (GSH) transferase (hGSTP1-1) processes with similar kinetic efficiencies the antitumor agents 2-crotonyloxymethyl-2-cyclohexenone (COMC-6), 2-crotonyloxymethyl-2-cycloheptenone (COMC-7), and 2-crotonyloxymethyl-2-cyclopentenone (COMC-5) to 2-glutathionylmethyl-2-cyclohexenone, 2-glutathionylmethyl-3-glutathionyl-2-cycloheptenone, and 2-glutathionylmethyl-2-cyclopentenone, respectively. This process likely involves initial enzyme-catalyzed Michael addition of GSH to the COMC derivative to give a glutathionylated enol(ate), which undergoes nonstereospecific ketonization, either while bound to the active site or free in solution, to a glutathionylated exocyclic enone. Free in solution, GSH reacts at the exomethylene carbon of the exocyclic enone, displacing the first GSH to give the final product. This mechanism is supported by the observation of multiphasic kinetics in the presence of high concentrations of hGSTP1-1 and the ability to trap kinetically competent exocyclic enones in aqueous acid using COMC-6 and COMC-7 as substrates. That the exocyclic enone is formed by nonstereospecific ketonization of an enol(ate) species is indicated by the observation that COMC-6 (chirally labeled with deuterium at the exomethylene carbon) gives stereorandomly labeled exocyclic enone. The isozymes hGSTP1-1, hGSTA1-1, hGSTA4-4, and hGSTM2-2 catalyze the conversion of COMC-6 to final product with similar efficiencies (K(m) = 0.08-0.34 mM, k(cat) = 1.5-6.1 s(-)(1)); no activity was detected with the rat rGSTT2-2 isozyme. Molecular docking studies indicate that in hGSTP1-1, the hydroxyl group of Tyr108 might serve as a general acid catalyst during substrate turnover. The possible significance of these observations with respect to the metabolism of COMC derivatives in multidrug resistant tumors is discussed.     

Theoretical investigation of Mössbauer hyperfine interactions in ordered FeNi and disordered Fe–Ni alloys

Electronic structure spin-polarized calculations were performed for 79-atoms embedded clusters representing the ordered intermetallic compound FeNi, the fcc Fe-rich disordered alloy Fe₈₅Ni₁₅ in an antiferromagnetic (AFM) configuration, and the ferromagnetic (FM) disordered alloy Fe₅₀Ni₅₀. The spin-polarized discrete variational method (DVM) in Density Functional theory was employed. Spin magnetic moments, as well as the ⁵⁷Fe Mössbauer hyperfine parameters isomer shift and magnetic hyperfine fields, were obtained from the calculations. For FM Fe₅₀Ni₅₀, the effect of pressure on the hyperfine field and on the isomer shift was investigated, for three different local atomic configurations surrounding the ⁵⁷Fe probe atom. In the case of the isomer shift, the calculated values were compared to reported experimental data.     

Direct-on-filter analysis of crystalline silica using photoacoustic Fourier transform-infrared spectroscopy

Photoacoustic Fourier transform-infrared spectroscopy (PA-FT-IR) has been used to perform direct-on-filter (DOF) analysis of crystalline silica using laboratory-generated filter samples. With these samples, the silica particles were embedded in the stable three-dimensional matrix of the filter. In this preliminary study, it was demonstrated that the photoacoustic (PA) signals generated from direct-on-filter measurements were significantly higher than the corresponding signals for equivalent amounts of silica particles placed directly in the photoacoustic detector cup. Studies with Min-U-Sil-5 loaded onto 9 mm filter stubs indicated a limit of detection of less than 10 μg. Additionally, Teflon filters were demonstrated to be more suitable for these measurements than other types. The photoacoustic FT-IR approach seems to be feasible for further development to use with full-sized personal sampling filters.     

Construction of fiber-optic bundle light-collection systems and calculations of collection efficiency

This paper describes the position-sensitive light-collection system that we use in our fast-beam laser experiments. The collection system consists of fiber-optic bundles whose facets are arranged to accept light emitted from a beam of fluorescent atoms. The flexibility of the fiber bundles allows their use in scanning collection systems with precise position sensitivity. We describe calculations of geometrical collection efficiency using a numerical integration scheme and compare the results with measurements. We also compare the collection efficiencies of the different fiber bundle arrangements that we used as our apparatus evolved with the implementation of various improvements.     

Lacton-Bildung durch ringerweiternde Fragmentierung von Epoxycyclodecanon-Derivaten

Lactones from Epoxycyclodecanone Derivatives by Ring Enlargement Involving Fragmentation Reactions A stereospecific ring-enlargement reaction of alkyl esters of 2,3-epoxy-1-(3-hydroxypropyl)-10-oxocyclo-decanecarboxylic-acid derivatives is described, involving Grob fragmentation of in situ formed hemiacetals. The assignment of the relative configuration of the starting materials was accomplished on the basis of ¹H-NMR data. The rearrangement of the epoxides 9 and 10 (with cis-orientation of the ester group and the epoxide ring, Scheme 1) gives the lactone 15 as the single and as the major product, respectively, with (Z)-configuration of the newly formed C?C bond. A concerted reaction mechanism is assumed. The formation of a small amount of 12 from 10 is probably due to a competitive two-step carbanion pathway. The reaction of the diastereoisomers 7 and 8 leads to the lactones 11 and 12 , respectively, as the only ring-enlargement products (Scheme 1), with (E)-configuration of the newly formed C?C bond. On the basis of our results, we cannot distinguish in this case between a concerted and a two-step carbanion mechanism. This type of reaction takes place only in the presence of an ester group; no ring enlargement was detected in case of compound 20 (Scheme 3), which is the de(alkoxycarbonyl) derivative of 9 . The eliminative opening of the epoxide ring in the epoxylactone 17 affords 11 as the single product (Scheme 2). A carbanion mechanism was assumed for this reaction.