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T. Andrew Mobley Eleanor G. Tennyson Grant S. Hisao 《Magnetic resonance in chemistry : MRC》2010,48(10):787-792
Recently reported triple‐resonance Y‐relayed 1H,X correlation experiments have been utilized to characterize 183W and 57Fe chemical shifts using 119Sn as the Y‐relaying nucleus instead of the previously used 31P. Application of an adaptation of Gudat's original INEPT/HMQC sequence results in a significant enhancement of the signal‐to‐noise (S/N) ratio for two‐dimensional 119Sn‐relayed 1H,183W and 1H, 57Fe correlation spectra with efficient detection of the transition metal nucleus in tungsten and iron complexes lacking an observable direct scalar coupling between the transition metal and any hydrogen nuclei. Strengths and shortcomings of the novel sequence and the original sequences reported by Gudat are discussed in the context of 119Sn‐relayed proton detection of very low frequency transition metal nuclei. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
43.
Naijing Su Juliana A. Theorell Prof. Dr. Donald J. Wink Prof. Dr. Tom G. Driver 《Angewandte Chemie (International ed. in English)》2015,54(44):12942-12946
The combination of 20 mol % of copper iodide and lithium tert‐butoxide triggers the formation of a broad range of substituted, functionalized α‐alkoxy 2H‐naphthalenones from readily available N‐tosylhydrazones. The data suggests that this transformation occurs through cycloaddition of a copper carbenoid with an ester, followed by a Lewis acid‐catalyzed [1,2] alkyl shift of the in situ generated alkoxyepoxide intermediate. 相似文献
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Klimovich Pavel V. Shirts Michael R. Mobley David L. 《Journal of computer-aided molecular design》2015,29(5):397-411
Journal of Computer-Aided Molecular Design - Free energy calculations based on molecular dynamics simulations show considerable promise for applications ranging from drug discovery to prediction of... 相似文献
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Classroom teachers need a well‐developed deep understanding of fractions and pedagogic practices so they can provide meaningful experiences for students to explore and construct ideas about fractions. This study sought to examine prospective elementary teachers' understandings of fraction by focusing specifically on their use of fractions meanings and interpretations. Results indicated that prospective elementary teachers bring with them to their final methods course a limited understanding of fractions and that experiences in methods courses resulted only in minor improvement of those limited understandings. The limited part‐whole understanding of fractions that prospective elementary teachers entered the course with was resilient. The implications of this study suggest a need for prospective elementary teachers to continue to develop their conceptual understanding of fractions and for changes to the content and instructional strategies of mathematics content courses designed for prospective elementary teachers. 相似文献
48.
Camilla Abbehausen Juliana F. CastroMarcelle B.M. Spera Tassiele A. HeinrichClaudio M. Costa-Neto Wilton R. LustriAndré L.B. Formiga Pedro P. Corbi 《Polyhedron》2011,30(13):2354-2359
A new gold(I) complex with 2-mercaptothiazoline (MTZ) with the coordination formula [AuCN(C3H5NS2)] was synthesized and characterized by chemical and spectroscopic measurements, DFT studies and biological assays. Infrared (IR) and 1H, 13C and 15N nuclear magnetic resonance (NMR) spectroscopic measurements indicate coordination of the ligand to gold(I) through the nitrogen atom. Studies based on DFT confirmed nitrogen coordination to gold(I) as a minimum of the potential energy surface with calculations of the hessians showing no imaginary frequencies. Thermal decomposition starts at temperatures near 160 °C, leading to the formation of Au0 as the final residue at 1000 °C. The gold(I) complex with 2-mercaptothiazoline (Au-MTZ) is soluble in dimethyl sulfoxide (DMSO), and is insoluble in water, methanol, ethanol, acetonitrile and hexane. The antibacterial activities of the Au-MTZ complex were evaluated by an antibiogram assay using the disc diffusion method. The compound showed an effective antibacterial activity against Staphylococcus aureus (Gram-positive) and Escherichia coli and Pseudomonas aeruginosa (Gram-negative) bacterial cells. Biological analysis for evaluation of the cytotoxic effect of the Au-MTZ complex was performed using HeLa cells derived from human cervical adenocarcinoma. The complex presented a potent cytotoxic activity, inducing 85% of cell death at a concentration of 2.0 μmol L−1. 相似文献
49.
This study investigated the effect of A-type cranberry proanthocyanidins (AC-PACs) on osteoclast formation and bone resorption activity. The differentiation of human pre-osteoclastic cells was assessed by tartrate-resistant acid phosphatase (TRAP) staining, while the secretion of interleukin-8 (IL-8) and matrix metalloproteinases (MMPs) was measured by ELISA. Bone resorption activity was investigated by using a human bone plate coupled with an immunoassay that detected the release of collagen helical peptides. AC-PACs up to 100 μg/mL were atoxic for osteoclastic cells. TRAP staining evidenced a dose-dependent inhibition of osteoclastogenesis. More specifically, AC-PACs at 50 μg/mL caused a 95% inhibition of RANKL-dependent osteoclast differentiation. This concentration of AC-PACs also significantly increased the secretion of IL-8 (6-fold) and inhibited the secretion of both MMP-2 and MMP-9. Lastly, AC-PACs (10, 25, 50 and 100 μg/ml) affected bone degradation mediated by mature osteoclasts by significantly decreasing the release of collagen helical peptides. This study suggests that AC-PACs can interfere with osteoclastic cell maturation and physiology as well as prevent bone resorption. These compounds may be considered as therapeutic agents for the prevention and treatment of periodontitis. 相似文献
50.
Páez-Hernández D Murillo-López JA Arratia-Pérez R 《The journal of physical chemistry. A》2011,115(32):8997-9003
A systematic study of a series of An(COT)(2) compounds, where An = Th, Pa, U, and COT represents cyclooctatetraene, has been performed using relativistic density functional theory. The ZORA Hamiltonian was applied for the inclusion of relativistic effects, taking into account all of the electrons for the optimization and explicitly including spin-orbit coupling effects. Time-dependent density functional theory (TDDFT) was used to calculate the excitation energies with the GGA SAOP functional, and the electronic transitions were analyzed using double group irreducible representations. The calculated excitation energies are in perfect correlation with the increment of the ring delocalization as it increases along the actinide series. These results are sufficient to ensure that, for these complexes, the increment in delocalization, as indicated by ELF bifurcation and NICS analysis, leads to a shift in the maximum wavelength of absorption in the visible region. Also, delocalization in the COT ring increases along the actinide series, so the systems become more aromatic because of a modulation induced by the actinides. 相似文献