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51.
Dr. Kely Navakoski de Oliveira Vincent Andermark Susanne von Grafenstein Liliane A. Onambele Gregor Dahl Riccardo Rubbiani Prof. Dr. Gerhard Wolber Dr. Chiara Gabbiani Prof. Dr. Luigi Messori Prof. Dr. Aram Prokop Prof. Dr. Ingo Ott 《ChemMedChem》2013,8(2):256-264
Thioredoxin reductase (TrxR) is overexpressed in cancer cells and is therefore a putative cancer target. Inhibition of this enzyme is considered an important strategy for the development of new chemotherapeutic agents with a specific mechanism of action. Organotin compounds have been described as experimental antitumor agents, yet their mechanism of action remains largely unknown. Based on the outcome of a virtual screening study, various di‐ and tri‐n‐butyltin(IV) carboxylates were synthesized, and their biological properties were evaluated. All synthesized compounds were able to inhibit TrxR selectively within the micromolar range and showed potent antitumor activity against HT‐29 and MCF‐7 cancer cell lines. Moreover, tin(IV) organometallics were found to strongly induce apoptosis in the BJAB lymphoma cell line. Mass spectrometry and atomic absorption spectroscopy experiments revealed metal binding to proteins, and efficient cellular uptake was observed using a di‐n‐butyltin(IV) complex as an example. 相似文献
52.
Dr. Madina Mansurova Julian Simon Dr. Susanne Salzmann Prof. Dr. Christel M. Marian Prof. Dr. Wolfgang Gärtner 《Chembiochem : a European journal of chemical biology》2013,14(5):645-654
Two chemically synthesized flavin derivatives, 8‐trifluoromethyl‐ and 8‐bromoriboflavin (8‐CF3RF and 8‐BrRF), were photochemically characterized in H2O and studied spectroscopically after incorporation into the LOV domain of the blue light photoreceptor YtvA from Bacillus subtilis. The spectroscopic studies were paralleled by high‐level quantum chemical calculations. In solution, 8‐BrRF showed a remarkably high triplet quantum yield (0.97, parent compound riboflavin, RF: 0.6) and a small fluorescence quantum yield (0.07, RF: 0.27). For 8‐CF3RF, the triplet yield was 0.12, and the fluorescence quantum yield was 0.7. The high triplet yield of 8‐BrRF is due to the bromine heavy atom effect causing a stronger spin–orbit coupling. Theoretical calculations reveal that the decreased triplet yield of 8‐CF3RF is due to a smaller charge transfer and a less favorable energetic position of T2, required for intersystem crossing from S1 to T1, as an effect of the electron‐withdrawing CF3 group. The reconstitution of the LOV domain with the new flavins resulted in the typical LOV photochemistry, consisting of triplet state formation and covalent binding of the chromophore, followed by a thermal recovery of the parent state, albeit with different kinetics and photophysical properties. 相似文献
53.
Concentration effects in water condensation systems, such as used in the water-based condensation particle counter, are explored through numeric modeling and direct measurements. Modeling shows that the condensation heat release and vapor depletion associated with particle activation and growth lowers the peak supersaturation. At higher number concentrations, the diameter of the droplets formed is smaller, and the threshold particle size for activation is higher. This occurs in both cylindrical and parallel plate geometries. For water-based systems, we find that condensational heat release is more important than vapor depletion. We also find that concentration effects can be minimized through use of smaller tube diameters, or more closely spaced parallel plates. Experimental measurements of droplet diameter confirm modeling results. © 2013 American Association for Aerosol Research 相似文献
54.
Susanne V. Hering Bruce R. Appel W. Cheng F. Salaymeh Steven H. Cadle Patricia A. Mulawa 《Aerosol science and technology》2013,47(1):200-213
Measurement methods for fine particle carbon were compared under field sampling conditions. Sampling methods included filtration, impaction, and adsorption-corrected filtration. Systems were operated side-by-side for nine consecutive days in the Los Angeles Basin. Analytical methods were compared separately. For organic carbon and total carbon, ambient measurements showed greater variability than could be accounted for by differences in analytical methods, and these differences are attributed to sampling methodology. The highest reported concentrations were obtained by quartz filter sampling; the lowest were from the sum of the impactor stages (excluding the quartz afterfilters). Positive artifact from the adsorption of gaseous vapors on quartz fiber filters was significant. However, correction for vapor adsorption by subtraction of the carbon value on the second of two filters in series did not completely eliminate the dependence of the apparent total aerosol carbon concentration on filter face velocity or sample duration 相似文献
55.
A Method for Particle Size Amplification by Water Condensation in a Laminar,Thermally Diffusive Flow
A new method is presented for the enlargement of particle size through condensation of water vapor in a laminar, thermally diffusive flow. The method involves the introduction of an air flow at temperature T i into a wet-walled tube at a temperature Tw > Ti . This approach yields higher supersaturation values than either mixing or cold-walled condensers when operating between the same temperature extremes. Model results for the saturation profiles within the condensing region show that the peak supersaturations are reached along the centerline of the flow, and that the activation efficiency curves are steeper for large temperature differences when the cutpoint diameter is smaller. Experiments conducted with three types of aerosol, oleic acid (a water-insoluble oil), a mixture of oxalic acid and sulfate, and with ambient laboratory aerosol confirmed that condensational growth is achieved with this approach, although experimental cutpoints are somewhat higher than predicted for wettable particles. 相似文献
56.
Susanne V. Hering Nathan M. Kreisberg Mark R. Stolzenburg Gregory S. Lewis 《Aerosol science and technology》2013,47(1):86-96
As part of the California Regional PM 2.5 and PM 10 Air Quality Study (CRPAQS) particle size distributions were measured simultaneously at two sites; the city of Fresno and the agricultural site of Angiola. Reported here are data obtained by scanning mobility analysis over the size range from 10 nm to 400 nm for the intensive study period from December 1, 2000 through February 6, 2001. These high time resolution data show variability in the character of the distributions, as well as the in the total number concentrations. The most pronounced feature of the data set is a consistent, nighttime maxima in particle number concentrations with a modal diameter near 80 nm during the evening hours at the urban Fresno site. Although these maxima are correlated with CO, NO, and black carbon, the particle size is larger than the 30–40 nm modal diameters observed for traffic aerosols during the commute hours, and is attributed to a non-vehicle source. At the agricultural site, the morning maxima particle number concentration coincides with the maxima in NO concentration, but often precedes the morning maxima in black carbon. Values for the geometric mean particle diameter varied from day to day, but are correlated between the two sites, with somewhat larger particle sizes at Angiola during periods of stagnation. 相似文献
57.
Köhler K Lellouch AC Vollmer S Stoevesandt O Hoff A Peters L Rogl H Malissen B Brock R 《Chembiochem : a European journal of chemical biology》2005,6(1):152-161
Cellular signal transduction proceeds through a complex network of molecular interactions and enzymatic activities. The timing of these molecular events is critical for the propagation of a signal and the generation of a specific cellular response. To define the timing of signalling events, we introduce the combination of high-resolution confocal microscopy with the application of small-molecule inhibitors at various stages of signal transduction in T cells. Inhibitors of Src-family tyrosine kinases and actin dynamics were employed to dissect the role of the lymphocyte-specific tyrosine kinase Lck in the formation and maintenance of T cell receptor/CD3-dependent contacts. Anti-CD3epsilon-coated coverslips served as a highly defined stimulus. The kinetics of the recruitment of the yellow fluorescent protein-tagged signalling protein ZAP-70 were detected by high-resolution confocal microscopy. The analysis revealed that at 5 min after receptor engagement, Lck activity was required for maintenance of contacts. In contrast, after 20 min of receptor engagement, the contacts were Lck-independent. The relevance of the timing of inhibitor application provides a pharmacological concept for the maturation of T cell-substrate contacts. 相似文献
58.
Funke SA Otte N Eggert T Bocola M Jaeger KE Thiel W 《Protein engineering, design & selection : PEDS》2005,18(11):509-514
Chiral compounds can be produced efficiently by using biocatalysts. However, wild-type enzymes often do not meet the requirements of a production process, making optimization by rational design or directed evolution necessary. Here, we studied the lipase-catalyzed hydrolysis of the model substrate 1-(2-naphthyl)ethyl acetate both theoretically and experimentally. We found that a computational equivalent of alanine scanning mutagenesis based on QM/MM methodology can be applied to identify amino acid positions important for the activity of the enzyme. The theoretical results are consistent with concomitant experimental work using complete saturation mutagenesis and high-throughput screening of the target biocatalyst, a lipase from Bacillus subtilis. Both QM/MM-based calculations and molecular biology experiments identify histidine 76 as a residue that strongly affects the catalytic activity. The experiments demonstrate its important influence on enantioselectivity. 相似文献
59.
60.
This paper deals with the competing risks model as a special case of a multi-state model. The properties of the model are reviewed and contrasted to the so-called latent failure time approach. The relation between the competing risks model and right-censoring is discussed and regression analysis of the cumulative incidence function briefly reviewed. Two real data examples are presented and a guide to the practitioner is given. 相似文献