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61.
How to confirm identified toxicants in effect-directed analysis 总被引:1,自引:0,他引:1
Brack W Schmitt-Jansen M Machala M Brix R Barceló D Schymanski E Streck G Schulze T 《Analytical and bioanalytical chemistry》2008,390(8):1959-1973
Due to the production and use of a multitude of chemicals in modern society, waters, sediments, soils and biota may be contaminated
with numerous known and unknown chemicals that may cause adverse effects on ecosystems and human health. Effect-directed analysis
(EDA), combining biotesting, fractionation and chemical analysis, helps to identify hazardous compounds in complex environmental
mixtures. Confirmation of tentatively identified toxicants will help to avoid artefacts and to establish reliable cause–effect
relationships. A tiered approach to confirmation is suggested in the present paper. The first tier focuses on the analytical
confirmation of tentatively identified structures. If straightforward confirmation with neat standards for GC–MS or LC–MS
is not available, it is suggested that a lines-of-evidence approach is used that combines spectral library information with
computer-based structure generation and prediction of retention behaviour in different chromatographic systems using quantitative
structure–retention relationships (QSRR). In the second tier, the identified toxicants need to be confirmed as being the cause
of the measured effects. Candidate components of toxic fractions may be selected based, for example, on structural alerts.
Quantitative effect confirmation is based on joint effect models. Joint effect prediction on the basis of full concentration–response
plots and careful selection of the appropriate model are suggested as a means to improve confirmation quality. Confirmation
according to the Toxicity Identification Evaluation (TIE) concept of the US EPA and novel tools of hazard identification help
to confirm the relevance of identified compounds to populations and communities under realistic exposure conditions. Promising
tools include bioavailability-directed extraction and dosing techniques, biomarker approaches and the concept of pollution-induced
community tolerance (PICT).
Figure Toxicity confirmation in EDA as a tiered approach 相似文献
62.
Checkers R. Marshall Emma E. Timmel Sara A. Staudhammer Carl K. Brozek 《Chemical science》2020,11(42):11539
Nanoparticles of metal–organic frameworks (nanoMOFs) boast superior properties compared to their bulk analogs, yet little is known about how common synthetic parameters dictate particle sizes. Here, we provide experimental evidence for the “seesaw” model of nanoMOF growth. Solution acidity, ligand excess, and reactant concentrations are decoupled and shown to form the key independent determinants of nanoMOF sizes, thereby validating the proposal that nanoMOFs arise from coupled equilibria involving ligand deprotonation and metal–ligand complexation. By achieving the first demonstration of a seesaw relationship between nanoMOF sizes and ligand excess, these results provide further proof of the model, as they required deliberate manipulation of relationships outlined by the model. Exploring the relative impacts of these parameters reveals that ligand excess has the greatest ability to decrease sizes, although low acidity and high concentrations can exhibit similar effects. As a complement to existing models of polymer formation and crystal growth, the seesaw model therefore offers a powerful tool for reliable control over nanoMOF sizes.Nanoparticles of metal–organic frameworks (nanoMOFs) boast superior properties compared to their bulk analogs, yet little is known about how common synthetic parameters dictate particle sizes. 相似文献
63.
Melander C Andersson E Axelsson S Gorton L 《Analytical and bioanalytical chemistry》2007,387(7):2585-2593
A novel method for detection of reducing ends of sugars is proposed, based on the use of as the oxidant in combination with amperometric detection and flow injection analysis (FIA). The method is very sensitive,
giving values of <10 μM for the limit of detection for a series of mono- and oligosaccharides. Samples can be analysed every
30 s, and injection can be made fully automated, making it possible to perform on-line analysis of polysaccharide samples
subjected to hydrolysis. Three methylcelluloses (MC) of different qualities were hydrolysed with three different glucanases,
and the concentrations of reducing ends prior to, during and after hydrolysis were determined. Differences were observed between
the results obtained using different combinations of enzymes and MCs, which revealed different selectivities of the various
enzymes for the different substrates. One MC was also hydrolysed and analysed in real-time for three hours. The method proposed
is superior to many of the standard methods used today, which require manual labour and have a lower sensitivity.
Figure Set-up used for the instrumentation in the FIA system with automated injection. A pump delivers the reaction solution to the
autosampler, where the samples are injected; the sample and solution react in a temperature-controlled random coil and the
response is detected using an amperometric detection cell 相似文献
64.
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66.
Chemical investigations of the Australian marine sponge Ecionemia geodides resulted in the isolation of two new pyridoacridine alkaloids, ecionines A (1) and B (2), along with the previously isolated marine natural products, biemnadin (3) and meridine (4). Compounds 1 and 2 both contain an imine moiety, which is rare for the pyridoacridine structure class. The chemical structures of 1 and 2 were determined by extensive 1D and 2D NMR and MS data analyses. All compounds were tested against a panel of human bladder cancer cell lines, the increasingly metastatic TSU-Pr1 series (TSU-Pr1, TSU-Pr1-B1 and TSU-Pr1-B2) and the superficial bladder cancer cell line 5637. Ecionine A (1) displayed cytotoxicity against all cell lines, with IC50 values ranging from 3 to 7 μM. This is the first report of chemistry from the sponge genus Ecionemia. 相似文献
67.
Eduardo Laborda Emma I. Rogers Francisco Martínez‐Ortiz Ángela Molina Richard G. Compton 《Electroanalysis》2010,22(23):2784-2793
The application of additive differential pulse voltammetry to the study of the kinetics of a charge transfer process is studied. A simple analytical solution is presented, valid for spherical electrodes of any size and for electrode processes of any reversibility. From this solution, valuable diagnostic criteria for the elucidation of the electrochemical reversibility are established based on the variation of the ADPV signal with the duration of the potential pulses, the electrode radius and the pulse height. Working curves for the determination of the kinetic parameters are also given. The value of the ADPV technique is experimentally demonstrated by studying the kinetics of the reduction of 3‐nitrophenolate? and europium3+ at mercury hemispherical microelectrodes. 相似文献
68.
Emma E. McCabe 《Journal of solid state chemistry》2010,183(3):624-143
The new phases Ba2LaMNb4O15: M=Mn, Fe were prepared by solid state reaction at 1100 °C. They have the tetragonal tungsten bronze structure, space group P4/mbm, at room temperature. The two octahedral sites show partial order of M and Nb with preferential occupancy of the smaller B(1) sites by M. Both phases have high permittivities 90±15 over the range 10-320 K. Ba2LaFeNb4O15 is highly insulating with bulk conductivity ?10−8 ohm−1 cm−1 at 25 °C and tan δ?0.001 over the range 100-320 K and at 105 Hz. Solid solutions between these new phases and the compositionally and structurally related relaxor ferroelectric Ba2LaTi2Nb3O15 show gradual loss of ferroelectric behaviour attributed to replacement of polarisable Ti4+ by a mixture of (Mn, Fe)3+ and Nb5+. 相似文献
69.
Yunsen Li Emma Arigi Heather Eichert Steven B. Levery 《Journal of mass spectrometry : JMS》2010,45(5):504-519
A method for generation of novel fluorocarbon derivatives of glycosphingolipids (GSLs) with high affinity for fluorocarbon phases has been developed, and their potential applications to mass spectrometry (MS)‐based methodologies for glycosphingolipidomics have been investigated. Sphingolipid ceramide N‐deacylase (SCDase) is used to remove the fatty acid from the ceramide moiety, after which a fluorocarbon‐rich substituent (F‐Tag) is incorporated at the free amine of the sphingoid. In initial trials, a neutral GSL, globotriaosylceramide (Gb3Cer), three purified bovine brain gangliosides, and four fungal glycosylinositol phosphorylceramides (GIPCs) were de‐N‐acylated, derivatized by prototype F‐Tags, and recovered by solid phase extraction on fluorocarbon‐derivatized silica (F‐SPE). The efficacy of SCDase treatment of GIPCs was here demonstrated for the first time. Compatibility with subsequent per‐N,O‐methylation was established for the F‐tagged Gb3 Cer and purified gangliosides, and extensive mass spectra (MS1 and MS2) consistent with all of the expected products were acquired. The potential use of F‐tagged derivatives for a comprehensive MS based profiling application was then demonstrated on a crude ganglioside mixture extracted from bovine brain. Finally, a simple trial in microarray format demonstrated fixation of F‐tagged GM1 ganglioside to a fluorous glass surface, with the glycan intact and available for interaction with a fluorescent derivative of cholera toxin B chain. The methods described thus provide a new avenue for rapid GSL recovery or cleanup, potentially compatible with a variety of platforms for mass spectrometric profiling and structure analysis, as well as parallel analysis of functional interactions. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
70.
Wallace EV Stoddart D Heron AJ Mikhailova E Maglia G Donohoe TJ Bayley H 《Chemical communications (Cambridge, England)》2010,46(43):8195-8197
Two DNA bases, 5-methylcytosine (5mC) and 5-hydroxymethylcytosine (hmC), marks of epigenetic modification, are recognized in immobilized DNA strands and distinguished from G, A, T and C by nanopore current recording. Therefore, if further aspects of nanopore sequencing can be addressed, the approach will provide a means to locate epigenetic modifications in unamplified genomic DNA. 相似文献