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71.
72.
Celenligil-Cetin R Paraskevopoulou P Lalioti N Sanakis Y Staples RJ Rath NP Stavropoulos P 《Inorganic chemistry》2008,47(23):10998-11009
Redox events involving both metal and ligand sites are receiving increased attention since a number of biological processes direct redox equivalents toward functional residues. Metalloradical synthetic analogues remain scarce and require better definition of their mode of formation and subsequent operation. The trisamido-amine ligand [(RNC6H4)3N]3-, where R is the electron-rich 4-t-Bu Ph, is employed in this study to generate redox active residues in manganese and chromium complexes. Solutions of [(L1)Mn(II)-THF]- in THF are oxidized by dioxygen to afford [(L1re-1)Mn(III)-(O)2-Mn(III)(L1 re-1)]2-as the major product. The rare dinuclear manganese (III,III) core is stabilized by a rearranged ligand that has undergone an one-electron oxidative transformation, followed by retention of the oxidation equivalent as a pi radical in ano-diiminobenzosemiquinonate moiety. Magnetic studies indicate that the ligand-centered radical is stabilized by means of extended antiferromagnetic coupling between the S ) 1/2 radical and the adjacent S ) 2 Mn(III) site, as well as between the two Mn(III) centers via the dioxo bridge. Electrochemical and EPR data suggest that this system can store higher levels of oxidation potency. Entry to the corresponding Cr(III) chemistry is achieved by employing CrCl3 to access both[(L1)Cr(III)-THF] and [(L1re-1)Cr(III)-THF(Cl)], featuring the intact and the oxidatively rearranged ligands, respectively. The latter is generated by ligand-centered oxidation of the former compound. The rearranged ligand is perceived to be the product of an one-electron oxidation of the intact ligand to afford a metal-bound aminyl radical that subsequently mediates a radical 1,4-(N-to-N) aryl migration. 相似文献
73.
Möbius Aromatic Core‐Modified Heterocyclic [20] Macrocycles (4.1.1) with a Protruding N‐Methyl Pyrrole Ring 下载免费PDF全文
Herein, we report the first synthesis of an unorthodox tripyrrane moiety from the regioselective β‐benzoylation of pyrrole and the acid‐catalyzed condensation of the desired precursors. A [3+1] Mac Donald type condensation strategy for this tripyrrane has led to the exclusive isolation of two hitherto‐unknown aromatic [20] heterocyclic macrocycles (4.1.1). 相似文献
74.
In this paper, necessary and sufficient conditions for the oscillation and asymptotic behaviour of solutions of the second
order neutral delay differential equation (NDDE)
are obtained, where q, h ∈ C([0, ∞), ℝ) such that q(t) ≥ 0, r ∈ C
(1) ([0, ∞), (0, ∞)), p ∈ C ([0, ∞), ℝ), G ∈ C (ℝ, ℝ) and τ ∈ ℝ+. Since the results of this paper hold when r(t) ≡ 1 and G(u) ≡ u, therefore it extends, generalizes and improves some known results.
相似文献
75.
As a part of a program for developing new efficient procedures for stereoselective glycosylation, a range of S-benzoxazolyl (SBox) glycosides have been synthesized. The mechanistic aspects of the SBox moiety activation for glycosylation via a variety of conceptually different pathways in the presence of thiophilic, electrophilic, or metal-based promoters have been investigated. 相似文献
76.
Katona BW Rath NP Anant S Stenson WF Covey DF 《The Journal of organic chemistry》2007,72(24):9298-9307
Deoxycholic acid (DCA) is an endogenous secondary bile acid implicated in numerous pathological conditions including colon cancer formation and progression and cholestatic liver disease. DCA involvement in these disease processes results partly from its ability to modulate signaling cascades within the cell, presumably through both direct receptor activation and general detergent mediated membrane changes. To further explore DCA induced changes in cell signaling, we completed a total synthesis of enantiomeric deoxycholic acid (ent-DCA) from achiral 2-methyl-1,3-cyclopentanedione. Using a modified method of the synthesis of ent-testosterone that proceeds through the (R)-(-)-Hajos-Parrish ketone, we have completed the successful synthesis of ent-DCA in 25 steps with a yield of 0.3% with all stereochemical assignments of the product confirmed by X-ray crystallography. Our studies toward this synthesis also uncovered the methodology for the development of a novel A,B-cis steroidal skeleton system containing a C3-C9 single bond as well as conditions to selectively ketalize the typically less reactive 12-carbonyl in poly-keto A,B-cis androgens. The critical micelle concentration (cmc) of ent-DCA, determined by a dye solubilization method, was identical to the cmc of natural DCA. Toxicity studies toward HT-29 and HCT-116 human colon cancer cell lines demonstrated that ent-DCA had similar effects on proliferation, yet showed a markedly decreased ability to induce apoptosis as compared to natural DCA. 相似文献
77.
The one‐sided lid‐driven cavity has been studied quite extensively as benchmark problem in CFD. In the present study we discus the stability of two‐dimensional flows with respect to three‐dimensional perturbations of a more general lid‐driven cavity with two moving walls facing each other. We show that, in addition to the known elliptic‐instability branch around aspect ratio 1.5, another branch of the elliptic instability exists for aspect ratios smaller unity. For high and around unit aspect ratio the instabilities are found to be of centrifugal and quadripolar type, respectively. The structure of critical modes as well as the instability mechanism are addressed. Additionally, the numerical results are compared to experimental results of [5]. 相似文献
78.
A forced liquid flow through an open capillary channel with free liquid surfaces is investigated. Since the free surfaces can only withstand a certain difference between the liquid pressure and the ambient pressure the flow rate in the channel is limited. The maximum flow rate is achieved when the surfaces collapse. A theoretical approach is presented which shows that the limitation of flow rate occurs due to choking. This theory confirms the results of an experiment performed on board the sounding rocket TEXUS‐37 to measure the maximum stationary volume flux of a forced flow through an open capillary channel. 相似文献
79.
Morelos A Albuquerque IF Bondar NF Carrigan RA Chen D Cooper PS Dai Lisheng Denisov AS Dobrovolsky AV Dubbs T Endler AM Escobar CO Foucher M Golovtsov VL Gottschalk H Gouffon P Grachev VT Khanzadeev AV Kubantsev MA Kuropatkin NP Lach J Lang Pengfei Li Chengze Li Yunshan Luksys M Mahon JR McCliment E Newsom C Pommot Maia MC Samsonov VM Schegelsky VA Shi Huanzhang Smith VJ Tang Fukun Terentyev NK Timm S Tkatch II Uvarov LN Vorobyov AA Yan Jie Zhao Wenheng Zheng Shuchen Zhong Yuanyuan 《Physical review letters》1993,71(14):2172-2175
80.