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131.
G. Schulze J. Drost G. D. Elsdon J. R. Stubbs 《Analytical and bioanalytical chemistry》1930,80(9-10):397-398
132.
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
133.
Ludden MJ Mulder A Schulze K Subramaniam V Tampé R Huskens J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(7):2044-2051
In this paper the multivalent binding of hexahistidine (His6)-tagged proteins to beta-cyclodextrin (beta-CD) self-assembled monolayers (SAMs) by using the nickel(II) complex of a hetero-divalent orthogonal adamantyl nitrilotriacetate linker (4) is described. Nonspecific interactions were suppressed by using monovalent adamantyl-hexa(ethylene glycol) derivative 3. With the mono-His6-tagged maltose binding protein (His6-MBP), thermodynamic modeling based on surface plasmon resonance (SPR) titration data showed that the MBP molecules in solution were linked, on average, to Ni.4 in 1:1 stoichiometry. On the surface, however, the majority of His(6)-MBP was complexed to surface-immobilized beta-CDs through three Ni.4 complexes. This difference is explained by the high effective beta-CD concentration at the surface and is a new example of supramolecular interfacial expression. In a similar adsorption scheme, SPR proved that the alpha-proteasome could be attached to beta-CD SAMs in a specific manner. Patterning through microcontact printing of (His6)4-DsRed-fluorescent timer (DsRed-FT), which is a tetrameric, visible autofluorescent protein, was carried out in the presence of Ni.4 Fluorescence measurements showed that the (His6)4-DsRed-FT is bound strongly through Ni.4 to the molecular printboard. 相似文献
134.
Janine Wolf Camino M. González Tanarro Michael Gütschow Joachim Sieler Bärbel Schulze 《Helvetica chimica acta》2008,91(1):35-45
The synthesis of novel triaryl‐substituted 4‐(isothiazol‐3‐yl)morpholines 7 and 8 , and 1‐(isothiazol‐3‐yl)piperazines 9 – 13 by reaction of the corresponding isothiazolium salts 5 and 6 with secondary amines in the presence of t‐BuOK in absolute THF is described. Some representatives of the isothiazoles were evaluated as inhibitors of acetylcholinesterase from Electrophorus electricus. 相似文献
135.
Two photon excited (TPE) fluorescence detection was applied to native fluorescence detection of aromatics in microchip electrophoresis (MCE). This technique was evaluated as an alternative to common one photon excitation in the deep UV spectral range. TPE enables fluorescence detection of unlabeled aromatic compounds, even in non-deep UV-transparent microfluidic chips. In this study, we demonstrate the proof of concept of native TPE fluorescence detection of small aromatics in commercial microfluidic glass chips. Label-free TPE fluorescence detection of native proteins and small aromatics in MCE was achieved within the micromolar concentration range, utilising 420 nm excitation light. 相似文献
136.
137.
Schulze Isfort C Kreickmann T Pape T Fröhlich R Hahn FE 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(8):2344-2357
The benzene-o-dithiol/catechol ligands H4-2 and H4-3 react with [TiO(acac)2] to give the dinuclear, double-stranded anionic complexes [Ti2(L)2(mu-OCH3)2](2-) ([22](2-), L=2(4-); [23](2-), L=3(4-)). NMR spectroscopic investigations reveal that the complex anion [Ti2(2)2(mu-OCH3)(2)](2-) is formed as a mixture of three of four possible isomers/pairs of enantiomers, whereas only one isomer of the complex anion [Ti2(3)2(mu-OCH3)(2)](2-) is obtained. The crystal structure analysis of (PNP)2[Ti2(3)2(mu-OCH3)2] shows a parallel orientation of the ligand strands, whereas the structure determination for (AsPh4)2[Ti2(2)2(mu-OCH3)2] does not yield conclusive results about the orientation of the ligand strands due the presence of different isomers in solution, the possible co-crystallisation of different isomers and severe disorder in the crystal. NMR spectroscopy shows that ligand H4-3 reacts at elevated temperature with [TiO(acac)2] to give the triple-stranded helicate (PNP)4[Ti2(3)3] ((PNP)4[24]) as a mixture of two isomers, one with a parallel orientation of the ligand strands and one with an antiparallel orientation. Exclusively the triple-stranded helicates [Ti2(L)(3)](4-) ([25](4-), L=1(4-); [26](2-), L=4(4-)) are formed in the reaction of ligands H4-1 and H4-4 with [TiO(acac)2]. The molecular structures of Na(PNP)3[Ti2(1)3]CH(3)OHH(2)OEt(2)O (Na(PNP)3[25]CH(3)OHH(2)OEt(2)O) and Na(1.5)(PNP)(6.5)[Ti2(4)3]2.3 DMF (Na(1.5)(PNP)(6.5)[26]2.3 DMF) reveal a parallel orientation of the ligand strands in both complexes, which is retained in solution. The sodium cations present in the crystal structures lead to two different kinds of aggregation in the solid state. Na-[25]-Na-[25]-Na polymeric chains are formed from compound Na(PNP)3[25], with the sodium cations coordinated by the carbonyl groups of two ligand strands from two different [Ti2(1)3](4-) ions in addition to solvent molecules. In contrast to this, two [Ti2(4)3](4-) ions are connected by a sodium cation that is coordinated by the three meta oxygen atoms of the catecholato groups of each complex tetraanion to form a central {NaO6} octahedron in the anionic pentanuclear complex {[26]-Na-[26]}(7-). 相似文献
138.
Antipina MN Schulze I Dobner B Langner A Brezesinski G 《Langmuir : the ACS journal of surfaces and colloids》2007,23(7):3919-3926
Cationic liposomes/DNA complexes can be used as nonviral vectors for direct delivery of DNA-based biopharmaceuticals to damaged cells and tissues. In order to obtain more effective and safer liposome-based gene transfection systems, the new cationic lipid 2-amino-3-hexadecyloxy-2-(hexadecyloxymethyl)propan-1-ol (AHHP) was synthesized. In this paper we report on the synthesis of AHHP and investigations of its physical-chemical properties. Langmuir monolayers of AHHP were studied at the air/buffer interface by film balance measurements, grazing incidence X-ray diffraction (GIXD), and infrared reflection absorption spectroscopy (IRRAS). Structure and thermotropic phase behavior of AHHP in aqueous dispersion were examined by small-angle and wide-angle X-ray scattering (SAXS/WAXS) and differential scanning calorimetry (DSC). The results show clear differences in structure and phase behavior of AHHP, both in the monolayer system and in aqueous dispersions, in dependence on the subphase pH due to protonation or deprotonation of the primary amine in the lipid head group. Thermodynamic data derived from pi-A isotherms provide information about the critical temperature (Tc), which is in rough agreement with the temperature of the lipid phase transition from gel to fluid state (Tm) found by X-ray and calorimetry studies of AHHP aqueous dispersions. The packing properties of the molecules in mono- and bilayer systems are very similar. DNA couples to the monolayer of the new lipid at low as well as at high pH but in different amounts. The DNA coupling leads to an alignment of adsorbed DNA strands indicated by the appearance of a Bragg peak. The distance between aligned DNA strands does not change much with increasing monolayer pressure. 相似文献
139.
A. Milekhin N.P. Stepina A.I. Yakimov A.I. Nikiforov S. Schulze D.R.T. Zahn 《The European Physical Journal B - Condensed Matter and Complex Systems》2000,16(2):355-359
Self-organised Ge dot superlattices grown by molecular beam epitaxy of Ge and Si layers utilizing Stranski-Krastanov growth
mode were investigated by Raman spectroscopy. An average size of Ge quantum dots was obtained from transmission electron microscopy
measurements. The strain and interdiffusion of Ge and Si atoms in Ge quantum dots were estimated from the analysis of frequency
positions of optical phonons observed in the Raman spectra. Raman scattering by folded longitudinal acoustic phonons in the
Ge dot superlattices was observed and explained using of elastic continuum theory.
Received 25 January 2000 相似文献
140.
We introduce the algebra of smoothing Mellin and Green symbols in a pseudodifferential calculus for manifolds with edges. In addition, we define scales of weighted Sobolev spaces with asymptotics based on the Mellin transform and analyze the mapping properties of the operators on these spaces. This will allow us to obtain complete information on the regularity and asymptotics of solutions to elliptic equations on these spaces. 相似文献