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761.
A cell-microelectronic sensing technique is developed for profiling chemical cytotoxicity and is used to study different cytotoxic effects of the same class chemicals using nitrosamines as examples. This technique uses three human cell lines (T24 bladder, HepG2 liver, and A549 lung carcinoma cells) and Chinese hamster ovary (CHO-K1) cells in parallel as the living components of the sensors of a real-time cell electronic sensing (RT-CES) method for dynamic monitoring of chemical toxicity. The RT-CES technique measures changes in the impedance of individual microelectronic wells that is correlated linearly with changes in cell numbers during t log phase of cell growth, thus allowing determination of cytotoxicity. Four nitrosamines, N-nitrosodimethylamine (NDMA), N-nitrosodiphenylamine (NDPhA), N-nitrosopiperidine (NPip), and N-nitrosopyrrolidine (NPyr), were examined and unique cytotoxicity profiles were detected for each nitrosamine. In vitro cytotoxicity values (IC50) for NDPhA (ranging from 0.6 to 1.9 mM) were significantly lower than the IC50 values for the well-known carcinogen NDMA (15-95 mM) in all four cell lines. T24 cells were the most sensitive to nitrosamine exposure among the four cell lines tested (T24 > CHO > A549 > HepG2), suggesting that T24 may serve as a new sensitive model for cytotoxicity screening. Cell staining results confirmed that administration of the IC50 concentration from the RT-CES experiments inhibited cell growth by 50% compared to the controls, indicating that the RT-CES method provides reliable measures of IC50. Staining and cell-cycle analysis confirmed that NDPhA caused cell-cycle arrest at the G0/G1 phase, whereas NDMA did not disrupt the cell cycle but induced cell death, thus explaining the different cytotoxicity profiles detected by the RT-CES method. The parallel cytotoxicity profiling of nitrosamines on the four cell lines by the RT-CES method led to the discovery of the unique cytotoxicity of NDPhA causing cell-cycle arrest. This study demonstrates a new approach to comprehensive testing of chemical toxicity. 相似文献
762.
The development and characterization of one rat monoclonal antibody (mAb) for 2,4-dinitroaniline and of two rat mAbs for 2,6-dinitroaniline
are described. With the immunization of rats with 2,4,6-trinitrophenyl-glycylglycine–keyhole limpet hemocyanine (KLH) conjugate
one mAb (PK 5H6) has been developed and formatted into a competitive enzyme-linked immunosorbent assay (ELISA). This assay
no. 1 is very sensitive for 2,4-dinitroaniline with a test midpoint of 0.24 ± 0.06 μg L−1 (n = 19) in 40 mM phosphate-buffered saline (PBS). A second hapten, 3-(4-amino-2,6-dinitrophenyl)propionic acid, which was also
conjugated to KLH and used for the immunization of rats, led to two sensitive ELISAs for 2,6-dinitroaniline in 40 mM PBS with
test midpoints of 0.61 ± 0.08 μg L−1 (n = 15; mAb DNT4 3C6; assay no. 2) and 0.94 ± 0.29 μg L−1 (n = 17; mAb DNT4 1A7, assay no. 3). Selectivities of all mAbs were checked with more than 20 compounds, including nitroaromatic
compounds, 2,6-dinitroaniline pesticides, and other substituted derivatives of aniline. As very noticeable cross-reactivities,
all mAbs recognize 2-chloro-4,6-dinitroaniline, 4-chloro-2,6-dinitroaniline and 2-bromo-4,6-dinitroaniline, the last of these
being a major metabolite of the azo dye Disperse Blue 79. As first demonstrations of applications, two ELISAs (assays no.
1 and 2) were used for the analysis of 2,4- or 2,6-dinitroaniline in spiked water and soil samples. Recovery data were determined
and the majority of these data were in the range of 90–120%. These assays can contribute to a very cost-effective and environmentally
friendly immunochemical surveillance monitoring of environmental samples for contaminations with these compounds. To the best
of the authors’ knowledge, these are the first antibodies described for 2,4-dinitroaniline and for 2,6-dinitroaniline. 相似文献
763.
Jrg Gloede Sigrid Ozegowski Iris Keitel Klaus Buttke Margit Gruner Burkhard Costisella Wolfgang Pritzkow Holger Stephan Michael Bartoschek 《无机化学与普通化学杂志》2006,632(1):123-132
Two‐ and Threefold Intramolecular Brigdging p‐tert‐Butylcalix[8]arene Triphosphates – Synthesis, Structure and Stereochemistry [1] The phosphorylation of p‐tert‐butylcalix[8]arene ( 1 ) with phosphorus pentachloride and hydrolysis gives intramolecular bridging tert‐butylcalix[8]arene triphosphates. The reactivity (esterification, dehydratisation, complexation), the structure (nmr and x‐ray), and the stereochemical behaviour of the phosphates will be discussed. 相似文献
764.
Stephan Enthaler 《Tetrahedron letters》2006,47(46):8095-8099
For the first time in situ generated iron porphyrins have been applied as homogeneous catalysts for the transfer hydrogenation of ketones. Using 2-propanol as hydrogen source various ketones are reduced to the corresponding alcohols in good to excellent yield and selectivity. Under optimized reaction conditions high catalyst turnover frequencies up to 642 h−1 are achieved. 相似文献
765.
Photoinduced cycloadditions of N-methyl-1,8-naphthalenedicarboximide 1 with phenylacetylenes 2a-2c, cyclopropylacetylene 2d, diphenylacetylenes 2e-2f and 1-phenylpropyne 2g were investigated. In the case of phenylacetylenes 2a, 2b and cyclopropylacetylene 2c, photoreaction with 1 takes place at the naphthalene C(1)C(2) bond to give the cyclobutene products. For 4-methoxyphenylacetylene 1c, the cyclobutene 3c is obtained together with the 4-benzo[a]thebenidinone 4c derived from a primary oxetene product formed by [2+2] addition of the imide carbonyl with the alkyne. Similar to 2c, photocycloaddition of 1 with 2e and 2f gave the cyclobutenes 7e, 7f, 8f and the 4-benzo[a]thebenidinone products 9e, 9f and 10f, respectively, derived from the corresponding oxetenes. Photoreaction of 1 with 2g gave cyclobutene 7g and benzo[a]thebenidinone 9g. Sensitization experiment and internal heavy atom effect study showed that these reactions proceed from the ππ* singlet excited state of 1. Estimation of the free energy change for electron transfer between 11* and the alkynes and the calculation of charge and spin density distribution in the anion radical of 1 and the cation radical of the alkynes suggested that the cyclobutene products are formed by direct [2+2] cycloaddition of 11* with the alkyne, while the formation of the oxetene products is the result of electron transfer interaction between 11* and the alkyne. The regioselectivity in the oxetene formation is accounted for by charge and spin density distribution in the anion radical of 1 and the cation radical of the alkyne. 相似文献
766.
Stephan K. Pedersen Kristina Eriksen Nataliya N. Karaush‐Karmazin Boris Minaev Hans gren Gleb V. Baryshnikov Michael Pittelkow 《Angewandte Chemie (International ed. in English)》2020,59(13):5144-5150
We present a high‐yielding intramolecular oxidative coupling within a diazadioxa[10]helicene to give a dihydro‐diazatrioxa[9]circulene. This is the first [n]circulene containing more than eight ortho‐annulated rings (n>8). The single‐crystal X‐ray structure reveals a tight columnar packing, with a proton from a pendant naphthalene moiety centred directly above the central nine‐membered ring. This distinct environment induces a significant magnetic deshielding effect on that particular proton as determined by 1H NMR spectroscopy. The origin of the deshielding effect was investigated computationally in terms of the NICS values. It is established that the deshielding effect originates from an induced paratropic ring current from the seven aromatic rings of the [9]circulene structure, and is not due to the nine‐membered ring being antiaromatic. UV/Vis spectroscopy reveals more efficient conjugation in the prepared diazatrioxa[9]circulene compared to the parent helical azaoxa[10]helicenes, and DFT calculations, including energy levels, confirm the experimental observations. 相似文献
767.
768.
Using single molecule polarization spectroscopy, we investigated the alignment of a polymer solute with respect to the liquid crystal (LC) director in an LC device while applying an external electric field. The polymer solute is poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (or MEH-PPV), and the LC solvent is 5CB. The electric field induces a change in the LC director orientation from a planar alignment (no electric field) to a perpendicular (homeotropic) alignment with an applied field of 5.5 x 103 V/cm. We find that the polymer chains align with the LC director in both planar and homeotropic alignment when measured in the bulk of the LC solution away from the device interface. Single molecule polarization distributions measured as a function of distance from the LC device interface reveal a continuous change of the MEH-PPV alignment from planar to homeotropic. The observed polarization distributions are modeled using a conventional elastic model that predicts the depth profile of the LC director orientation for the applied electric field. The excellent agreement between experiment and simulations shows that the alignment of MEH-PPV follows the LC director throughout the LC sample. Furthermore, our results suggest that conjugated polymers such as MEH-PPV can be used as sensitive local probes to explore complex (and unknown) structures in anisotropic media. 相似文献
769.
770.