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111.
An enantioselective 1,2-chlorine atom migration was observed in the tributyltin hydride reduction of various dihalogenated dihydrocinnamic acid derivatives. It is proposed that the reduction involves the formation of a chlorine-bridged radical intermediate, followed by hydrogen atom transfer to either the beta- or the alpha-carbon. The product distribution is affected by electron-withdrawing groups in that hydrogen atom transfer to the proximate carbon is favored. Presumably, this is due to the transition state of the hydrogen delivery step being electron rich, due to the relatively electropositive tin radical. These results demonstrate a 1,2-chlorine atom migration reaction governed by polar effects. 相似文献
112.
Yoon TH Trainor TP Eng PJ Bargar JR Brown GE 《Langmuir : the ACS journal of surfaces and colloids》2005,21(10):4503-4511
The distributions of Pb(II) and As(V)O4(3-) ions in the interfacial region between thin poly(acrylic acid) (PAA) coatings and aalpha-A12O3(0001), alpha-Al2O3(1-102), and alpha-Fe2O3(0001) single-crystal substrates were studied using long-period X-ray standing wave fluorescent yield (XSW-FY) and X-ray reflectivity techniques. The PAA film serves as a simplified analogue of natural organic matter (NOM) coatings on mineral surfaces. Such coatings are often assumed to play an important role in the partitioning and speciation of trace heavy metals in soils and aquatic systems. On the alpha-Al2O3(1-102) surface, Pb(II) ions were found to preferentially bind to the PAA coating, even at sub-micromolar Pb(II) concentrations, and to partition increasingly onto the metal oxide surface as the Pb(II) concentration was increased ([Pb(II)] = 5 x 10(-8) to 2 x 10(-5) M, pH = 4.5; 0.01 M NaCl background electrolyte). This observation suggests that the binding sites in the PAA coating outcompete those on the alpha-Al2O3(1-102) surface for Pb(II) under these conditions. The As(V)O4(3-) oxoanion partitions preferentially to the L-Al2O3(1-102) surface for the As(V)O4(3-) concentrations examined (1 x 10(-7) to 5 x 10(-7) M, pH = 4.5; 0.01 M NaCl background electrolyte). Partitioning of Pb(II) (at 1 x 10(-7) M and pH 4.5) was also examined at PAA/alpha-Al2O3(0001), and PAA/alpha-Fe2O3(0001) interfaces using XSW-FY measurements. Our results show that the PAA coating was the dominant sink for Pb(II) in all three samples; however, the relative order of reactivity of these metal oxide surfaces with respect to Pb(II) sorption is alpha-Fe2O3(0001) > alpha-Al2O3(1-102) > alpha-Al2O3(0001). This order is consistent with that found in previous studies of the PAA-free surfaces. These XSW results strongly suggest that the characteristics of the organic film (i.e., binding affinity, type, and density of binding sites) as well as metal oxide substrate reactivity are key factors determining the distribution and speciation of Pb(II) and As(V)O4(3-) at organic film/metal oxide interfaces. 相似文献
113.
Pressurized liquid extraction (PLE) and pressurized hot water extraction (PHWE) using a laboratory-made system are applied for the extraction of thermally labile components such as tanshinone I and IIA in Salvia miltiorrhiza. PLE and PHWE are carried out dynamically at a flow of 1 mL/min, temperature between 95-140 degrees C, applied pressure of 10-20 bars, and extraction times of 20 and 40 min, respectively. Effects of ethanol added into the water used in PHWE are explored. PLE is found to give comparable or higher extraction efficiencies compared with PHWE with reference to Soxhlet extraction for tanshinone I and IIA in Salvia miltiorrhiza. The tanshinone I and IIA present in the various medicinal plant extracts are determined by liquid chromatography and liquid chromatography-mass spectrometry. 相似文献
114.
Westerlund F Pierard F Eng MP Nordén B Lincoln P 《The journal of physical chemistry. B》2005,109(36):17327-17332
The quenching of the luminescence of [Ru(phen)(2)dppz](2+) by structural homologue [Ru(phendione)(2)dppz](2+), when both complexes are bound to DNA, has been studied for all four combinations of Delta and Lambda enantiomers. Flow linear dichroism spectroscopy (LD) indicates similar binding geometries for all the four compounds, with the dppz ligand fully intercalated between the DNA base pairs. A difference in the LD spectrum observed for the lowest-energy MLCT transition suggests that a transition, potentially related to the final localization of the excited electron to the dppz ligand in [Ru(phen)(2)dppz](2+), is overlaid by an orthogonally polarized transition in [Ru(phendione)(2)dppz](2+). This would be consistent with a low-lying LUMO of the phendione moiety of [Ru(phendione)(2)dppz](2+) that can accept the excited electron from [Ru(phen)(2)dppz](2+), thereby quenching the emission of the latter. The lifetime of excited Delta-[Ru(phen)(2)dppz](2+) is decreased moderately, from 664 to 427 ns, when bound simultaneously with the phendione complex to DNA. The 108 ns lifetime of opposite enantiomer, Lambda-[Ru(phen)(2)dppz](2+), is only shortened to 94 ns. These results are consistent with an average rate constant for electron transfer of approximately 1.10(6) s(-1) between the phenanthroline- and phendione-ruthenium complexes. At binding ratios close to saturation of DNA, the total emission of the two enantiomers is lowered equally much, but for the Lambda enantiomer, this is not paralleled by a decrease in luminescence lifetime. A binding isotherm simulation based on a generalized McGhee-von Hippel approach shows that the Delta enantiomer binds approximately 3 times stronger to DNA both for [Ru(phendione)(2)dppz](2+) and [Ru(phen)(2)dppz](2+). This explains the similar decrease in total emission, without the parallel decrease in lifetime for the Lambda enantiomer. The simulation also does not indicate any significant binding cooperativity, in contrast to the case when Delta-[Rh(phi)(2)bipy](3+) is used as quencher. The very slow electron transfer from [Ru(phen)(2)dppz](2+) to [Ru(phendione)(2)dppz](2+), compared to the case when [Rh(phi)(2)phen](3+) is the acceptor, can be explained by a much smaller driving free-energy difference. 相似文献
115.
George Eng Deborah Whalen Primrose Musingarimi John Tierney Michael DeRosa 《应用有机金属化学》1998,12(1):25-30
In the interest of developing a more effective fungicide to combat Dutch elm disease, our laboratories have synthesized several triphenyltin carboxylates and some 1:1 addition compounds of triphenyltin chloride using 2,3-disubstituted thiazolidin-4-ones as the ligand and screened them in vitro against Ceratocystis ulmi, the causative agent of Dutch elm disease, using a shake culture method. Elemental analyses and spectroscopic data indicate that the structures of the carboxy- lates in the solid state are monomeric with a tetrahedral tin atom with the exception of the furan-2-carboxylic acid derivative, which was found to be polymeric. The triphenyltin chloride adducts are trigonal-bipyramidal with the three phenyl groups in the equatorial plane. Far-infrared data indicate that the three phenyl groups are not co-planar. Screening results for both series of organotins indicate that these two classes of compounds are effective inhibitors of Ceratocystis ulmi, with the adducts having a higher activity. The furan-2-carboxylic acid derivative has a markedly decreased activity compared with the other carboxylates and this is attributed to its polymeric structure. © 1998 John Wiley & Sons, Ltd. 相似文献
116.
This paper reports the activity of four dibutyltin(IV)–N-arylidene-α-amino acid complexes against the National Cancer Institute (NCI) panel of 60 cell lines. The results indicated that three of the organotin complexes (C17H25NO3Sn, C18H27NO3Sn and C20H31NO3Sn) exhibit their highest cytotoxic effect on the NCI-522 (non-small cell lung cancer) cell line. The fourth complex, C21H27NO3Sn, exhibits its highest cytotoxic activity on the cell line RXF-631L (renal cancer). In general, a low to moderate cellular response was observed for all the organotin complexes, with at least one cell line in each subpanel of cells exhibiting a very low growth inhibition response to all the organotin complexes. The low-responding cell lines included HOP-62 (non-small lung cancer), DLD-1 (colon cancer), SF-539 (CNS cancer), SK-MEL-5 (melanoma), IGROV-1 (ovarian cancer) and RPMI-8226 (leukemia). The results also indicated that the compounds did not exhibit any significant subpanel activity and suggested that the compounds were not active in all the cell lines contained in any subpanel. The low to moderate activity of these compounds across the cell lines was attributed to the presence of nitrogen-bearing ligands which prevented the dissociation of the compound and the subsequent binding to DNA. © 1998 John Wiley & Sons, Ltd. 相似文献
117.
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119.
Bioactivities and Mode of Actions of Dibutyl Phthalates and Nocardamine from Streptomyces sp. H11809
Fauze Mahmud Ngit Shin Lai Siew Eng How Jualang Azlan Gansau Khairul Mohd Fadzli Mustaffa Chiuan Herng Leow Hasnah Osman Hasidah Mohd Sidek Noor Embi Ping-Chin Lee 《Molecules (Basel, Switzerland)》2022,27(7)
Dibutyl phthalate (DBP) produced by Streptomyces sp. exerted inhibitory activity against human GSK-3β (Hs GSK-3β) and Plasmodium falciparum 3D7 (Pf 3D7) malaria parasites. The current study aimed to determine DBP’s plausible mode of action against Hs GSK-3β and Pf 3D7. Molecular docking analysis indicated that DBP has a higher binding affinity to the substrate-binding site (pocket 2; −6.9 kcal/mol) than the ATP-binding site (pocket 1; −6.1 kcal/mol) of Hs GSK-3β. It was suggested that the esters of DBP play a pivotal role in the inhibition of Hs GSK-3β through the formation of hydrogen bonds with Arg96/Glu97 amino acid residues in pocket 2. Subsequently, an in vitro Hs GSK-3β enzymatic assay revealed that DBP inhibits the activity of Hs GSK-3β via mixed inhibition inhibitory mechanisms, with a moderate IC50 of 2.0 µM. Furthermore, the decrease in Km value with an increasing DBP concentration suggested that DBP favors binding on free Hs GSK-3β over its substrate-bound state. However, the antimalarial mode of action of DBP remains unknown since the generation of a Pf 3D7 DBP-resistant clone was not successful. Thus, the molecular target of DBP might be indispensable for Pf survival. We also identified nocardamine as another active compound from Streptomyces sp. H11809 chloroform extract. It showed potent antimalarial activity with an IC50 of 1.5 μM, which is ~10-fold more potent than DBP, but with no effect on Hs GSK-3β. The addition of ≥12.5 µM ferric ions into the Pf culture reduced nocardamine antimalarial activity by 90% under in vitro settings. Hence, the iron-chelating ability of nocardamine was shown to starve the parasites from their iron source, eventually inhibiting their growth. H11809相似文献
120.