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81.
Kristina Kotnik Tina Kosjek Uroš Krajnc Ester Heath 《Analytical and bioanalytical chemistry》2014,406(13):3179-3190
This study describes a procedure for determining eight benzophenone-derived compounds in surface waters and sediments. These include the pharmaceutical ketoprofen, its phototransformation products 3-ethylbenzophenone and 3-acetylbenzophenone, and five benzophenone-type ultraviolet (UV) filters. The proposed analytical method involves the pre-concentration of water samples by solid-phase extraction (SPE) and microwave-assisted extraction (MAE) of sediment samples followed by derivatization and analysis by gas chromatography–mass spectrometry. Different parameters were investigated to achieve optimal method performance. Recoveries of 91 to 96 % from water samples were obtained using HLB Oasis SPE cartridges, whereas MAE of sediments (30 min at 150 °C) gave recoveries of 80 to 99 %. Limits of detection were between 0.1 and 1.9 ng L?1 for water samples and from 0.1 to 1.4 ng g?1 for sediment samples. The developed method was applied to environmental samples and revealed the presence of UV filters in the majority of the surface waters with up to 690 ng L?1 of 2-hydroxy-4-methoxybenzophenone. By contrast, ketoprofen (≤2,900 ng L?1) and its degradation products (≤320 ng L?1) were found in only two rivers, both receiving wastewater treatment plant effluents. Sediment analysis revealed benzophenone to be present in concentrations up to 650 ng g?1, whereas concentrations of other compounds were considerably lower (≤32 ng L?1). For the first time, quantifiable amounts of two ketoprofen transformation products in the aqueous environment are reported. 相似文献
82.
83.
R. L. Heath 《Journal of Radioanalytical and Nuclear Chemistry》1998,233(1-2):81b-89
A program has been developed at the INEL to produce new enhanced editions of the original Gamma-ray Spectrum Catalogues for
presentation in electronic format. This program has produced the first version of the Catalogues in CD-ROM format and will
offer them on the Internet through the Gamma-ray Spectrometry Center Web Site at INEEL. The original content of the Catalogues
has been expanded to include integrated decay scheme drawings, tables of related decay data, and updated material on the techniques
of gamma-ray spectrometry. All of the original spectral plots, gamma-ray energy and intensity data, and text were converted
to digital format, related decay data from the Evaluated Nuclear Structure Data File (ENSDF) and decay scheme graphics were
then added, and all data converted to the Adobe Acrobat (PDF) format. Follow-on versions of the catalogues are being expanded
to include prompt neutron capture and n-n' spectra and spectra representing the response of large-volume Ge detectors. Large-volume
Ge detector spectra will be calculated, using Monte Carlo and parametric fitting techniques presently under development. Examples
of content and details of the advanced technology applied to produce these new volumes will be presented. Services and content
of the Gamma-ray Spectrometry Center Web Site will also be described. 相似文献
84.
Farré M Petrovic M Gros M Kosjek T Martinez E Heath E Osvald P Loos R Le Menach K Budzinski H De Alencastro F Müller J Knepper T Fink G Ternes TA Zuccato E Kormali P Gans O Rodil R Quintana JB Pastori F Gentili A Barceló D 《Talanta》2008,76(3):580-590
Comparability of monitoring data are essential for any meaningful assessment and for the management of environmental risks of emerging pollutants. The reliability and comparability of data at European level is often limited, because analytical methods for emerging pollutants are often not fully validated, not harmonized or not suitable for all relevant matrices. This paper describes a collaborative interlaboratory exercise for the analysis of non-steroidal anti-inflammatory drugs (NSAIDs) residues in freshwater and wastewater, held in the framework of the EU project "Network of reference laboratories for monitoring of emerging environmental pollutants" (NORMAN). The NSAID compounds selected in this study were ketoprofen, naproxen, ibuprofen and diclofenac. Thirteen laboratories distributed along nine European Countries (Austria, France, Germany, Greece, Italy, Slovak Republic, Slovenia, Spain, and Switzerland) took part in this exercise, 126 samples were analyzed and a total number of 473 values in duplicate were collected. Samples selected in this study include environmental water (river water and waste water) and artificial water (fortified environmental and distilled water) with different ranges of complexity. Two analytical methods were proposed by the organiser; one is based on the use of solid phase extraction (SPE) followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) and the second one is based on SPE followed by gas-chromatography-mass spectrometry (GC-MS), however, in the first round some different approaches were also admitted. The main goals of this interlaboratory comparison were to evaluate the available analytical schemes for NSAID analysis in natural waters, to evaluate the repeatability (r) and reproducibility (R) between participating laboratories, and to evaluate the influence of the analytical method and sample matrices on the results. 相似文献
85.
Broglin BL Andreu A Dhussa N Heath JA Gerst J Dudley B Holland D El-Kouedi M 《Langmuir : the ACS journal of surfaces and colloids》2007,23(8):4563-4568
The effects of the local environment on surface-enhanced Raman scattering (SERS) spectra utilizing gold, silver, and gold/silver striped nanorod array substrates was investigated. The arrays were fabricated using an electrochemical metal deposition into an anodic aluminum oxide template. The analyte chosen for this study was p-nitroso-N,N-dimethylaniline (p-NDMA), which has an electronic structure that is highly sensitive to its surrounding environment. Changes in the peak positions and peak ratios were used to probe the influence of water and the striping pattern on the SERS signal of p-NDMA. We present the results of the fabrication and characterization of the nanorod array substrates, as well as SERS spectra of p-NDMA in both polar and nonpolar environments and SERS spectra on a variety of striped nanorod arrays. The Raman data suggests that the p-NDMA molecule exists in a more polarized state when bound to the gold as compared to the silver rods. We have attempted to use these differences to determine whether the SERS signal predominantly arises from the tips of the rods or from the interior of the array. 相似文献
86.
Turner CH 《Langmuir : the ACS journal of surfaces and colloids》2007,23(5):2525-2530
The equilibrium conversion of a chemical reaction is known to be affected by its local environment. Various factors may alter reaction equilibria, including shifts in pressure or temperature, solvation, adsorption within porous materials, or the presence of an interface. Previously, reactive Monte Carlo simulations have been used to predict the equilibrium behavior of chemical reactions at vapor-liquid interfaces. Here, a route is tested for tuning the interfacial conversion of a Lennard-Jones dimerization reaction by adding surfactants to the vapor-liquid interface. Several temperatures are explored as well as several different surfactant models. Even with the addition of a small concentration of surfactants, the simulations predict significant shifts in the conversion at the interface. In general, the shifts in the conversion tend to be related to the values of the interfacial tension. 相似文献
87.
Dr. Samir Das Dr. Arundhati Nag JingXin Liang Dr. David N. Bunck Dr. Aiko Umeda Blake Farrow Matthew B. Coppock Deborah A. Sarkes Amethist S. Finch Heather D. Agnew Suresh Pitram Bert Lai Mary Beth Yu Dr. A. Katrine Museth Dr. Kaycie M. Deyle Bianca Lepe Frances P. Rodriguez‐Rivera Amy McCarthy Belen Alvarez‐Villalonga Ann Chen John Heath Dimitra N. Stratis‐Cullum Prof. James R. Heath 《Angewandte Chemie (International ed. in English)》2015,54(45):13219-13224
We describe a general synthetic strategy for developing high‐affinity peptide binders against specific epitopes of challenging protein biomarkers. The epitope of interest is synthesized as a polypeptide, with a detection biotin tag and a strategically placed azide (or alkyne) presenting amino acid. This synthetic epitope (SynEp) is incubated with a library of complementary alkyne or azide presenting peptides. Library elements that bind the SynEp in the correct orientation undergo the Huisgen cycloaddition, and are covalently linked to the SynEp. Hit peptides are tested against the full‐length protein to identify the best binder. We describe development of epitope‐targeted linear or macrocycle peptide ligands against 12 different diagnostic or therapeutic analytes. The general epitope targeting capability for these low molecular weight synthetic ligands enables a range of therapeutic and diagnostic applications, similar to those of monoclonal antibodies. 相似文献
88.
Dr. Joseph Becica Oliver R. J. Heath Cameron H. M. Zheng Prof. Dr. David C. Leitch 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17430-17434
Carboxylate esters have many desirable features as electrophiles for catalytic cross-coupling: they are easy to access, robust during multistep synthesis, and mass-efficient in coupling reactions. Alkenyl carboxylates, a class of readily prepared non-aromatic electrophiles, remain difficult to functionalize through cross-coupling. We demonstrate that Pd catalysis is effective for coupling electron-deficient alkenyl carboxylates with arylboronic acids in the absence of base or oxidants. Furthermore, these reactions can proceed by two distinct mechanisms for C−O bond activation. A Pd0/II catalytic cycle is viable when using a Pd0 precatalyst, with turnover-limiting C−O oxidative addition; however, an alternative pathway that involves alkene carbopalladation and β-carboxyl elimination is proposed for PdII precatalysts. This work provides a clear path toward engaging myriad oxygen-based electrophiles in Pd-catalyzed cross-coupling. 相似文献
89.
Bhavesh H. PatelScott F.A. Heath Andrew M. MasonAnthony G.M. Barrett 《Tetrahedron letters》2011,52(17):2258-2261
Thermolysis of 6,6′-(2-oxopropane-1,3-diyl)bis(2,2-dimethyl-4H-1,3-dioxin-4-one) in the presence of methanol gave a triketo-ester which subsequently aromatized to provide a synthetically useful homophthalate ester. Enolate C-acylation in the presence of diethylzinc was used to synthesize other double diketo-dioxinones, which on cyclization, aromatization and dioxinone ring opening gave novel double resorcylate derivatives. 相似文献
90.
Brittany L. Heath Rebecca A. Jockusch 《Journal of the American Society for Mass Spectrometry》2012,23(11):1911-1920
Knowledge of the structure of protein?Cligand complexes can aid in understanding their roles within complex biological processes. Here we use electrospray ionization (ESI) coupled to a Fourier transform ion cyclotron resonance mass spectrometer to investigate the noncovalent binding of the macrocycle cucurbit[7]uril (CB7) to bovine insulin. Recent condensed-phase experiments (Chinai et al., J. Am. Chem. Soc. 133:8810?C8813, 2011) indicate that CB7 binds selectively to the N-terminal phenylalanine of the insulin B-chain. Competition experiments employing ESI mass spectrometry to assess complex formation between CB7 and wild type insulin B-chain vs. a mutant B-chain, confirm that the N-terminal phenylalanine plays in important role in solution-phase binding. However, analysis of fragment ions produced by electron capture dissociation (ECD) of CB7 complexed to intact insulin and to the insulin B-chain suggests a different picture. The apparent gas-phase binding site, as identified by the ECD, lies further along the insulin B-chain. Together, these studies thus indicate that the CB7 ligand migrates in the ESI mass spectrometry analysis. Migration is likely aided by the presence of additional interactions between CB7 and the insulin B-chain, which are not observed in the crystal structure. While this conformational difference may result simply from the removal of solvent and addition of excess protons by the ESI, we propose that the migration may be enhanced by charge reduction during the ECD process itself because ion-dipole interactions are key to CB7 binding. The results of this study caution against using ECD-MS as a stand-alone structural probe for the determination of solution-phase binding sites. 相似文献