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91.
Anuva Samanta Bijan Kumar Paul Sankar Jana Nikhil Guchhait 《Photochemistry and photobiology》2010,86(5):1022-1029
The photophysical properties of 5-(4-fluorophenyl)-2-hydroxypyridine (FP2HP) at different pH and its fluorescence response toward different transition metal ions have been studied by steady-state absorption and emission spectroscopy in combination with quantum chemical calculations. Although keto-enol tautomerization is observed in the excited state, the molecule is weakly fluorescent due to the presence of electron-rich nitrogen atom and relatively electron-deficient fluorine atom, which may lead to photoinduced electron transfer process. In the presence of the transition metal ions, such as Zn2+, Cd2+, Hg2+, etc., the studied molecule exhibits changes in its absorption and emission properties. The present system shows fluorescence enhancement instead of usual quenching in presence of the transition metal ions, such as Fe2+ and Cu2+. Spectral observation leads to the interpretation that this structurally simple molecule can be effectively utilized as a chelation-enhanced fluorescence-based chemosensor for the detection of transition metal ions. The experimental findings corroborate well with theoretical calculations at Hartree–Fock level using 6-31G** and lanl2dz basis sets. 相似文献
92.
Hrdlovic P Donovalova J Stankovicova H Gaplovsky A 《Molecules (Basel, Switzerland)》2010,15(12):8915-8932
Absorption and fluorescence spectra of bichromophoric coumarins were investigated in different solvents and in polymer matrices. These bichromophoric coumarins were composed of a coumarin dimethylamino-substituted at position 7 or unsubstituted coumarin and phthalimide or a 1,8-naphthylimide linked with an iminomethyl bridge to the position 3 or 8 of the coumarin ring. Absorption spectra of 7-dimethylamino derivatives in position 3 of coumarin were quite similar, exhibiting broad bands around 430-440 nm like the parent compound 7-dimethylaminocoumarin-3-carbaldehyde. For coumarin derivatives substituted in position 8, the absorption maximum was shifted to shorter wavelength as for derivatives without position 7 dimethylamino substitution. The most intense fluorescence was observed for 7-(N,N-dimethylamino)-3-[(N-phtalimidoyl)iminomethyl]coumarin in polar solvent, while intense fluorescence was observed for 7-(N,N-dimethylamino)-3-[N-(1,3-dioxobenz[de]isoquinolinyl)iminomethyl]-coumarin in non polar solvent (chloroform), comparable with the fluorescence of 7-amino-4-methylcoumarin. Spectral measurements of bichromophoric coumarins in polymer matrices revealed that the maxima lies in between those for chloroform and methanol yielding more intense fluorescence then in solutions. Completely different solvent effects were observed for 7-(N,N-dimethylamino)-3-[N-(1,3-dioxobenz[de]isoquinolinyl)imino-methyl]coumarin and 7-(N,N-dimethylamino)-3-[(N-phtalimidoyl)iminomethyl]coumarin. With addition of polar methanol the intensity of fluorescence decreases, yielding a Stern-Volmer-like constant of 0.54 dm3 mol?1 for 7-(N,N-dimethylamino)-3-[N-(1,3-dioxo-benz[de]isoquinolinyl)iminomethyl]coumarin and an even higher one of 1.08 dm3·mol?1 for 7-dimethylaminocoumarin-3-carbaldehyde compared to the rather low one of 0.024 dm3 mol?1 for 7-amino-4-methylcoumarin. Contrary to this, addition of methanol under identical conditions brings about an increase in fluorescence intensity of 7-(N,N-dimethylamino)-3-[(N-phtalimidoyl)iminomethyl]coumarin (about 60-fold). The reasons for these different solvent effects are discussed. 相似文献
93.
Helena Řehulková Jana Chalupová Marek Šebela Pavel Řehulka 《Journal of mass spectrometry : JMS》2010,45(1):104-111
Peptide samples derived from enzymatic in‐gel digestion of proteins resolved by gel electrophoresis often contain high amount of salts originating from reaction and separation buffers. Different methods are used for desalting prior to matrix‐assisted laser desorption/ionization (MALDI) mass spectrometry (MS), e.g. reversed‐phase pipette tip purification, on‐target washing, adding co‐matrices, etc. As a suitable matrix for MALDI MS of peptides, α‐cyano‐4‐hydroxycinnamic acid (CHCA) is frequently used. Crystalline CHCA shows the ability to bind peptides on its surface and because it is almost insoluble in acidic water solutions, the on‐target washing of peptide samples can significantly improve MALDI MS signals. Although the common on‐target washing represents a simple, cheap and fast procedure, only a small portion of the available peptide solution is efficiently used for the subsequent MS analysis. The present approach is a combination of the on‐target washing principle carried out in a narrow‐end pipette tip (e.g. GELoader tip) and preconcentration of peptides from acidified solution by passing it through small CHCA crystals captured inside the tip on a glass microfiber frit. The results of MALDI MS analysis using CHCA‐tip peptide preconcentration are comparable with the use of homemade POROS R2 pipette tip microcolumns. Advantages and limitations of this approach are discussed. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
94.
Zachariasova M Cajka T Godula M Malachova A Veprikova Z Hajslova J 《Rapid communications in mass spectrometry : RCM》2010,24(22):3357-3367
The objective of the presented study was to develop and optimize a simple, high-throughput method for the control of 32 mycotoxins (Fusarium and Alternaria toxins, aflatoxins, ergot alkaloids, ochratoxins, and sterigmatocystin) in beer. Due to the broad range of their physicochemical properties, the sample preparation step was simplified as much as possible to avoid analyte losses. The addition of acetonitrile to beer samples enabled precipitation of abundant matrix components. The clean-up efficiency was controlled by ambient mass spectrometry employing a direct analysis in real time (DART) ion source. For determination of analytes, ultra-high-performance liquid chromatography hyphenated with high-resolution mass spectrometry utilizing an orbitrap (U-HPLC-orbitrapMS) or time-of-flight (TOFMS) technology was used. Because of significantly better detection capabilities of the orbitrap technology, the U-HPLC-orbitrapMS method was chosen as a determinative step and fully validated. To compensate matrix effects, matrix-matched calibration was employed. The lowest calibration levels for most of the target mycotoxins ranged from 1 to 8 μg L(-1) beer and the recoveries of analytes were in range from 86 to 124%. 相似文献
95.
Ondrej Lacina Jana UrbanovaJan Poustka Jana Hajslova 《Journal of chromatography. A》2010,1217(5):648-659
In this study, the potential of ultra-high-performance liquid chromatography coupled with the time-of-flight mass spectrometry (UHPLC–TOF MS) to enable rapid and comprehensive analysis of 212 pesticide residues in QuEChERS extracts obtained from four plant matrices has been investigated. Method optimization is discussed in detail. In addition to molecular adducts, also fragment ions were provided for all target pesticides, thus obtaining at least three identification points required by European Decision 2002/657/EC was achieved. To get maximum information on analytes present in the extracts, each sample was examined within two injections, the first in a positive and the next one in a negative ionization mode. Under UHPLC conditions, both analyses were completed within 24 min. For more than 96% of pesticides involved in this study, the limit of quantification was ≤10 μg/kg. As a part of the work, strategy enabling screening of non-target pesticides and their metabolites is demonstrated on analysis of real-life samples. 相似文献
96.
The inclusion-exclusion principle is one of the basic theorems in combinatorics. In this paper the inclusion-exclusion principle for IF-sets on generalized probability measures is studied. The basic theorems are proved. 相似文献
97.
We prove that a system of linear inequalities with interval-valued data is weakly solvable (each system obtained by fixing coefficeints in the intervals prescribed has a solution) if and only if it is strongly solvable (all such systems have a solution in common) and desribe an algorithm for checking strong solvability. 相似文献
98.
In this paper we deal with cover–incomparability graphs of posets, or briefly C–I graphs. These are graphs derived from posets as the edge-union of their cover graph and their incomparability graph. We answer two recently posed open questions. Which distance-hereditary graphs are C–I graphs? Which Ptolemaic (i.e. chordal distance-hereditary) graphs are C–I graphs? It follows that C–I graphs can be recognized efficiently in the class of all distance-hereditary graph whereas recognizing C–I graphs in general is known to be NP-complete. 相似文献
99.
100.
One of the objectives of the Intergeo project was to provide European mathematics teachers with ??good quality?? pedagogical material supporting the use of dynamic geometry software in classrooms. With this aim in view, an online repository/platform was developed to gather various dynamic geometry resources, based on the idea of a teachers?? community feeding the repository, (re)using available resources and sharing practices related to the use of dynamic geometry in classrooms. The repository is thus open to contributions of any user who can deposit, browse, download and use resources, which naturally raises the question how to handle the resource quality issue in such an open environment. This paper reports on the way we tackled this issue in the Intergeo project. We first explain what we mean by a ??good quality?? dynamic geometry resource. We then provide a rationale behind the design of a questionnaire, the main tool for resource quality reviews, which are at the core of the quality assessment process implemented in the repository. Several experiments carried out with groups of teachers in order to confront our research-based view of the resource quality with the teachers?? one and to observe teachers?? usages of the quality assessment process are also reported in the paper. The outcomes of these experiments highlight strengths and limitations of the resource quality assessment process. They also tend to show that the idea of involving teachers into the resource quality assessment is a promising way of stimulating the use of dynamic geometry in classrooms, provided that teachers benefit from a support to make the quality process their own. 相似文献