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The oxidation of an anticancer drug 5-fluorouracil (5-FU) by diperiodatoargentate(III) (DPA) was carried out both in the absence and presence of osmium(VIII) catalyst in alkaline medium at 27 °C and a constant ionic strength of 0.20 mol dm−3 spectrophotometrically attached with HI-TECH SFA-12 stopped flow accessory. The oxidation products in both the cases were identified as fluoroketene and Ag(I). The stoichiometry is same in both cases, i.e., [5-FU]:[DPA] = 1:1. The reaction was of first order in both catalysed and uncatalysed cases, with respect to [DPA] and was less than unit order in [5-FU] and negative fraction in [alkali]. The order in Os(VIII) was unity. In both cases [Ag(H3IO6)2] itself is the active species of DPA. The uncatalysed reaction in alkaline medium has been shown to proceed via a DPA-5-fluorouracil complex, which decomposes in a rate determining step to give the products. In catalysed reaction, it has been shown to proceed via a Os(VIII)-5-fluorouracil complex, which further reacts with one molecule of DPA in a rate determining step to give the products. The reaction constants involved in the different steps of the mechanisms were calculated for both the reactions. The catalytic constant (kCat.const.) was also calculated for catalysed reaction at different temperatures. The activation parameters with respect to slow step of the mechanisms were computed and discussed for both the cases. The thermodynamic quantities were also determined for both reactions.  相似文献   
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Tree‐ring records provide global high‐resolution information on tree‐species responses to global change, forest carbon and water dynamics, and past climate variability and extremes. The underlying assumption is a stationary (time‐stable), quasi‐linear relationship between tree growth and environment, which however conflicts with basic ecological and evolutionary theory. Indeed, our global assessment of the relevant tree‐ring literature demonstrates non‐stationarity in the majority of tested cases, not limited to specific proxies, environmental parameters, regions or species. Non‐stationarity likely represents the general nature of the relationship between tree‐growth proxies and environment. Studies assuming stationarity however score two times more citations influencing other fields of science and the science–policy interface. To reconcile ecological reality with the application of tree‐ring proxies for climate or environmental estimates, we provide a clarification of the stationarity concept, propose a simple confidence framework for the re‐evaluation of existing studies and recommend the use of a new statistical tool to detect non‐stationarity in tree‐ring proxies. Our contribution is meant to stimulate and facilitate discussion in light of our results to help increase confidence in tree‐ring‐based climate and environmental estimates for science, the public and policymakers.  相似文献   
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A series of chalcone-amidobenzothiazole conjugates (9a-k and 10a,b) have been synthesized and evaluated for their anticancer activity. All these compounds exhibited potent activity and the IC(50) of two potential compounds (9a and 9f) against different cancer cell lines are in the range of 0.85-3.3 μM. Flow cytometric analysis revealed that these compounds induced cell cycle arrest at G2/M phase in A549 cell line leading to caspase-3 dependent apoptotic cell death. The tubulin polymerization assay (IC(50) of 9a is 3.5 μM and 9f is 5.2 μM) and immuofluorescence analysis showed that these compounds effectively inhibit microtubule assembly at both molecular and cellular levels in A549 cells. Further, Annexin staining also suggested that these compounds induced cell death by apoptosis. Moreover, docking experiments have shown that they interact and bind efficiently with tubulin protein. Overall, the current study demonstrates that the synthesis of chalcone-amidobenzothiazole conjugates as promising anticancer agents with potent G2/M arrest and apoptotic-inducing activities via targeting tubulin.  相似文献   
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A series of benzothiazole and benzoxazole linked pyrrolobenzodiazepine conjugates attached through different alkane or alkylamide spacers was prepared. Their anticancer activity, DNA thermal denaturation studies, restriction endonuclease digestion assay and flow cytometric analysis in human melanoma cell line (A375) were investigated. One of the compounds of the series 17d showed significant anticancer activity with promising DNA-binding ability and apoptosis caused G0/G1 phase arrest at sub-micromolar concentrations. To ascertain the binding mode and understand the structural requirement of DNA binding interaction, molecular docking studies using gold program and more rigorous 2 ns molecular dynamic simulations using Molecular Mechanics-Poisson–Boltzman Surface Area (MM-PBSA) approach including the explicit solvent were carried out. Further, the compound 17d was evaluated for in vivo efficacy studies in human colon cancer HT29 xenograft mice.  相似文献   
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Climate warming is expected to enhance productivity and growth of woody plants, particularly in temperature‐limited environments at the northernmost or uppermost limits of their distribution. However, this warming is spatially uneven and temporally variable, and the rise in temperatures differently affects biomes and growth forms. Here, applying a dendroecological approach with generalized additive mixed models, we analysed how the growth of shrubby junipers and coexisting trees (larch and pine species) responds to rising temperatures along a 5000‐km latitudinal range including sites from the Polar, Alpine to the Mediterranean biomes. We hypothesize that, being more coupled to ground microclimate, junipers will be less influenced by atmospheric conditions and will less respond to the post‐1950 climate warming than coexisting standing trees. Unexpectedly, shrub and tree growth forms revealed divergent growth trends in all the three biomes, with juniper performing better than trees at Mediterranean than at Polar and Alpine sites. The post‐1980s decline of tree growth in Mediterranean sites might be induced by drought stress amplified by climate warming and did not affect junipers. We conclude that different but coexisting long‐living growth forms can respond differently to the same climate factor and that, even in temperature‐limited area, other drivers like the duration of snow cover might locally play a fundamental role on woody plants growth across Europe.  相似文献   
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Molecular Breeding - Molecular breeding is capable of improving important agricultural crop traits by controlling functional genes, aiming to attain high yield, stability and quality. During this...  相似文献   
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