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81.
A new type of berberine derivatives was obtained by the reaction of berberrubine with aliphatic sulfonyl chlorides. The new polycyclic compounds have a sultone ring condensed to C and D rings of a protoberberine core. The reaction conditions were developed to facilitate the formation of sultones with high yields without by-product formation. Thus, it was shown that the order of addition of reagents affects the composition of the reaction products: when sulfochlorides are added to berberrubine, their corresponding 9-O-sulfonates are predominantly formed; when berberrubine is added to pre-generated sulfenes, sultones are the only products. The reaction was shown to proceed stereo-selectively and the cycle configuration was confirmed by 2D NMR spectroscopy. The inhibitory activity of the synthesized sultones and their 12-brominated analogs against the DNA-repair enzyme tyrosyl-DNA phosphodiesterase 1 (Tdp1), an important target for a potential antitumor therapy, was studied. All derivatives were active in the micromolar and submicromolar range, in contrast to the acyclic analogs and 9-O-sulfonates, which were inactive. The significance of the sultone cycle and bromine substituent in binding with the enzyme was confirmed using molecular modeling. The active inhibitors are mostly non-toxic to the HeLa cancer cell line, and several ligands show synergy with topotecan, a topoisomerase 1 poison in clinical use. Thus, novel berberine derivatives can be considered as candidates for adjuvant therapy against cancer.  相似文献   
82.
Nanocomposite polymer electrolytes (NPEs) were synthesized using sodium alginate (Alg) and either sodium (SCa-3-Na+)- or lithium (SCa-3-Li+)-modified montmorillonite clays. The samples were characterized by structural, optical, and electrical properties. SCa-3-Na+ and SCa-3-Li+ clays’ X-ray structural analyses revealed peaks at 2θ = 7.2° and 6.7° that corresponded to the interlamellar distances of 12.3 and 12.8 Å, respectively. Alg-based NPEs X-ray diffractograms showed exfoliated structures for samples with low clay percentages. The increase of clay content promoted the formation of intercalated structures. Electrochemical Impedance Spectroscopy revealed that Alg-based NPEs with 5 wt% of SCa-3-Na+ clay presented the highest conductivity of 1.96 × 10−2 S/cm2, and Alg with 10 wt% of SCa-3-Li+ showed conductivity of 1.30 × 10−2 S/cm2, both measured at 70 °C. From UV-Vis spectroscopy, it was possible to infer that increasing concentration of clay promoted a decrease of the samples’ transmittance and, consequently, an increase of their reflectance.  相似文献   
83.
Brønsted acid-catalyzed inverse-electron demand (IED) aza-Diels-Alder reactions between 2-aza-dienes and ethylene were studied using quantum chemical calculations. The computed activation energy systematically decreases as the basic sites of the diene progressively become protonated. Our activation strain and Kohn-Sham molecular orbital analyses traced the origin of this enhanced reactivity to i) “Pauli-lowering catalysis” for mono-protonated 2-aza-dienes due to the induction of an asynchronous, but still concerted, reaction pathway that reduces the Pauli repulsion between the reactants; and ii) “LUMO-lowering catalysis” for multi-protonated 2-aza-dienes due to their highly stabilized LUMO(s) and more concerted synchronous reaction path that facilitates more efficient orbital overlaps in IED interactions. In all, we illustrate how the novel concept of “Pauli-lowering catalysis” can be overruled by the traditional concept of “LUMO-lowering catalysis” when the degree of LUMO stabilization is extreme as in the case of multi-protonated 2-aza-dienes.  相似文献   
84.
Journal of Structural Chemistry - A new cobalt(II) complex of 5-phenyl-3-(pyridin-2-yl)-1,2,4-triazine (PPTA), [Co(PPTA)2(NO3)2] (1), is prepared and identified by the elemental analysis, FTIR...  相似文献   
85.
A six-step synthesis towards a tribenzotriquinacene (TBTQ) bearing three quinoxalinophenanthrophenazine (QPP) units is presented. The optoelectronic properties are investigated and the effect of the three-dimensional arrangement of the individual QPP planes is examined using optical spectroscopy, electrochemical analysis and quantum-chemical calculations.  相似文献   
86.
JETP Letters - The structural and magnetic properties of the Co7Te8 layered compound have been studied for the first time using X-ray diffraction, measurements of the magnetic susceptibility, and...  相似文献   
87.
Moscow University Chemistry Bulletin - A piezoactive nanofiber composite PVDF film with TiO2 nanoparticles included in it was synthesized by electrospinning. The composition, morphology and...  相似文献   
88.
Experiments on crack identification in cantilever beams   总被引:1,自引:0,他引:1  
In this paper we present an experimental investigation of the identification of crack location and size. By providing the first three natural frequencies through vibration measurements, curves of crack equivalent stiffness versus crack location are plotted, and the intersection of the three curves predicts the crack location and size. In the experiments, the cracked specimens were made using a wire-cut electrical discharge machine, and the cantilever beams were excited next to the free end by means of an impulse force hammer. In order to obtain the accurate natural frequencies from the transient signal measured, the method of zoom fast Fourier transform is adopted to improve frequency resolution. From experimental results, it is observed that the identification errors of crack location and size are less than 2% and 4%, respectively. The effectiveness of crack identification through vibration measurements is verified.  相似文献   
89.
This study presents a quantitative evaluation of the influence of radiation upon the parameters of a long induced discharge in argon at atmospheric pressure. Radiation heat transfer in the optically transparent tin plasma layers with thickness of the order of several centimeters) and reabsorption spectral intervals is examined. Experimental error produced by inaccurate knowledge of the transfer and optical characteristics of the plasma is evaluated. The effect of convection on radial temperature profile is evaluated.Translated from Zhurnal Prikladnoi Mekhaniki i Tekhnicheskoi Fiztki, No. 6, pp. 35–43, November–December, 1971.  相似文献   
90.
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