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2.
Victoria A. Ternes Hannah A. Morgan Austin P. Lanquist Michael J. Murray Bradley M. Wile 《应用有机金属化学》2020,34(4):e5459
Herein we report the preparation of a series of Ru(II) complexes featuring α-iminopyridine ligands bearing thioether functionality (NNSR, where R = Me, CH2Ph, Ph). Metallation using [(p-cymene)RuCl]2 permits access to Ru complexes with a κ2-N,N donor set in which the thioether moiety remains uncoordinated. In the presence of a strong field ligand such as acetonitrile or triphenylphosphine, the p-cymene moiety is displaced, and the ligand adopts a κ3-N,N,S binding mode. These complexes are characterized using a combination of solution and solid state methods, including the crystal structure of [(NNSMe)Ru (NCMe)2Cl]Cl. The κ2-N,N-Ru(II) complexes are shown to serve as efficient precatalysts for the oxidation of sec-phenethyl alcohol at modest loadings (alcohol: Ru = 20:1), using a variety of external oxidants and solvents. The complex bearing an S-Ph donor was found to be the most active oxidation catalyst of those surveyed, suggesting that the thioether donor plays an active role in the catalytic cycle. 相似文献
3.
Bradley Currey Hartmut Führ Vignon Oussa 《Applied and Computational Harmonic Analysis》2019,46(3):500-543
This paper presents a full catalogue, up to conjugacy and subgroups of finite index, of all matrix groups that give rise to a continuous wavelet transform with associated irreducible quasi-regular representation. For each group in this class, coorbit theory allows to consistently define spaces of sparse signals, and to construct atomic decompositions converging simultaneously in a whole range of these spaces. As an application of the classification, we investigate the existence of compactly supported admissible vectors and atoms for the groups. 相似文献
4.
In this paper, we are interested in the following question: given an arbitrary Steiner triple system on vertices and any 3‐uniform hypertree on vertices, is it necessary that contains as a subgraph provided ? We show the answer is positive for a class of hypertrees and conjecture that the answer is always positive. 相似文献
5.
Anke Kuijk Arnout Imhof Margriet H. W. Verkuijlen Thijs H. Besseling Ernst R. H. van Eck Alfons van Blaaderen 《Particle & Particle Systems Characterization》2014,31(6):706-713
In this paper, the characterization and fluorescent labeling of silica rods are reported. These rods are synthesized following a recently reported method. Material properties of the silica rods measured with NMR, elemental analysis, TGA, and porosimetry are compared with those of well‐established Stöber silica spheres. Additionally, silica rods are made suitable for quantitative real‐space studies by confocal microscopy. Several methods of fluorescent labeling to prepare rods with different fluorescent patterning, ranging from uniform fluorescence levels to gradients from one rod‐end to the other, and even patterns of several colors are presented and discussed. 相似文献
6.
In this study we synthesized and characterized mirror image barnase (B. amyloliquefaciens ribonuclease). d-Barnase was identical to l-barnase, when analyzed by liquid chromatography and mass-spectrometry. Proteolysis of the mirror image enzyme revealed that in contrast to its native counterpart, d-barnase was completely stable to digestive proteases. In enzymatic assays, d-barnase had the reciprocal chiral specificity and was fully active towards mirror image substrates. Interestingly, d-barnase also hydrolyzed the substrate of the native chirality, albeit 4000 times less efficiently. This effect was further confirmed by digesting a native 112-mer RNA with the enzyme. Additional studies revealed that barnase accommodates a range of substrates with various chiralities, but the prime requirement for guanosine remains. These studies point toward using mirror image enzymes as modern agents in biotechnology. 相似文献
7.
In this paper we extend a central limit theorem of Peligrad for uniformly strong mixing random fields satisfying the Lindeberg condition in the absence of stationarity property. More precisely, we study the asymptotic normality of the partial sums of uniformly \(\alpha \)-mixing non-stationary random fields satisfying the Lindeberg condition, in the presence of an extra dependence assumption involving maximal correlations. 相似文献
8.
Robert D. Bradley Brennan D. McManus Jessalyn G. Yam Dr. Veronica Carta Dr. Ana Bahamonde 《Angewandte Chemie (International ed. in English)》2023,62(43):e202310753
This work demonstrates the dominance of a Ni(0/II/III) cycle for Ni-photoredox amide arylation, which contrasts with other Ni-photoredox C-heteroatom couplings that operate via Ni(I/III) self-sustained cycles. The kinetic data gathered when using different Ni precatalysts supports an initial Ni(0)-mediated oxidative addition into the aryl bromide. Using NiCl2 as the precatalyst resulted in an observable induction period, which was found to arise from a photochemical activation event to generate Ni(0) and to be prolonged by unproductive comproportionation between the Ni(II) precatalyst and the in situ generated Ni(0) active species. Ligand exchange after oxidative addition yields a Ni(II) aryl amido complex, which was identified as the catalyst resting state for the reaction. Stoichiometric experiments showed that oxidation of this Ni(II) aryl amido intermediate was required to yield functionalized amide products. The kinetic data presented supports a rate-limiting photochemically-mediated Ni(II/III) oxidation to enable C−N reductive elimination. An alternative Ni(I/III) self-sustained manifold was discarded based on EPR and kinetic measurements. The mechanistic insights uncovered herein will inform the community on how subtle changes in Ni-photoredox reaction conditions may impact the reaction pathway, and have enabled us to include aryl chlorides as coupling partners and to reduce the Ni loading by 20-fold without any reactivity loss. 相似文献
9.
Levi Evans Yiqui Shen Abigail Bender Leah E. Burnett Musheng Li Justine S. Habibian Tong Zhou Bradley S. Ferguson 《Molecules (Basel, Switzerland)》2021,26(5)
Plant-based foods, like fruits, vegetables, whole grains, legumes, nuts, seeds and other foodstuffs, have been deemed as heart healthy. The chemicals within these plant-based foods, i.e., phytochemicals, are credited with protecting the heart. However, the mechanistic actions of phytochemicals, which prevent clinical endpoints, such as pathological cardiac hypertrophy, are still being elucidated. We sought to characterize the overlapping and divergent mechanisms by which 18 selected phytochemicals prevent phenylephrine- and phorbol 12-myristate 13-acetate-mediated cardiomyocyte enlargement. Of the tested 18 compounds, six attenuated PE- and PMA-mediated enlargement of neonatal rat ventricular myocytes. Cell viability assays showed that apigenin, baicalein, berberine hydrochloride, emodin, luteolin and quercetin dihydrate did not reduce cell size through cytotoxicity. Four of the six phytochemicals, apigenin, baicalein, berberine hydrochloride and emodin, robustly inhibited stress-induced hypertrophy and were analyzed further against intracellular signaling and genome-wide changes in mRNA expression. The four phytochemicals differentially regulated mitogen-activated protein kinases and protein kinase D. RNA-sequencing further showed divergence in gene regulation, while pathway analysis demonstrated overlap in the regulation of inflammatory pathways. Combined, this study provided a comprehensive analysis of cardioprotective phytochemicals. These data highlight two defining observations: (1) that these compounds predominantly target divergent gene pathways within cardiac myocytes and (2) that regulation of overlapping signaling and gene pathways may be of particular importance for the anti-hypertrophic actions of these phytochemicals. Despite these new findings, future works investigating rodent models of heart failure are still needed to understand the roles for these compounds in the heart. 相似文献
10.
Dr. Robert J. Messinger Dr. Kyungsu Na Dr. Yongbeom Seo Prof. Dr. Ryong Ryoo Prof. Dr. Bradley F. Chmelka 《Angewandte Chemie (International ed. in English)》2015,54(3):927-931
Mesoporous zeolites are a new and technologically important class of materials that exhibit improved diffusion and catalytic reaction properties compared to conventional zeolites with sub‐nanometer pore dimensions. During their syntheses, the transient developments of crystalline and mesoscopic order are closely coupled and challenging to control. Correlated solid‐state NMR, X‐ray, and electron microscopy analyses yield new molecular‐level insights on the interactions and distributions of complicated organic structure‐directing agents with respect to crystallizing zeolite frameworks. The analyses reveal the formation of an intermediate layered silicate phase, which subsequently transforms into zeolite nanosheets with uniform nano‐ and mesoscale porosities. Such materials result from coupled surfactant self‐assembly and inorganic crystallization processes, the interplay between which governs the onset and development of framework structural order on different length and time scales. 相似文献