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131.
Jonathan W. Dube Prof. Paul J. Ragogna 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(35):11768-11775
The bis(phosphino)borate ligand class is used as an anionic anchor to stabilize reactive, low coordinate arsenic centers. The neutral, zwitterionic AsI species, 2 , is formed very cleanly, and isolated in good yields using cyclohexene as a halogen scavenger. The uniqueness of this heterocyclic AsI compound is on display with the coordination to Group 6 metal centers, ( 2 M(CO)5 ; M=Cr, Mo, W). The arsenic? metal bond lengths are longer than the related AsPh3 complexes suggesting that compound 2 is a weak sigma donor. The metal complexes reveal a trigonal pyramidal arsenic atom, which provides the first experimental evidence for the presence of two “lone pairs” of electrons on the AsI center. When more flexible and more electron‐donating isopropyl substituents were used, an intermediate (compound 5 ) in the formation of low coordinate pnictogen compounds was crystallographically characterized. This structure, formally a base‐stabilized dichloroarsenium cation, provides an alternative mechanistic proposal to the one described in the literature. 相似文献
132.
Combining isotope ratio monitoring with isotope dilution techniques provides very accurate results in the quantitative analysis of volatile organic chemical compounds by gas chromatography/mass spectrometry (GC/MS). However, this method requires that spikes highly enriched in (13)C be used. This may lead to memory effects which will be investigated in more detail. They occur when the component of the mixture to be investigated exhibits an isotope ratio which is different from that of the component eluted earlier from the column during the chromatographic separation process. A residue of this component, which is shown in the gas chromatogram as tailing, falsifies the result of the isotope ratio measurement. This also leads to false amount-of-substance measurement results. Memory effects can be avoided by using spikes of low (13)C content, by adjusting the composition of the reference solution to that of the sample, or by ensuring effective sample preparation, thus separating disturbing mixture components prior to the measurement. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
133.
134.
Cavitands and capsules define nanoliter spaces for recognition, isolation and reactions of small molecules. These systems are usually self-assembled and factors such as solvent size, stoichiometry, and packing factors determine what goes into the spaces. Here we examine two switching devices to control what and when guests get in and out of these hosts: bipyridyl-metal chelation and azobenzene photoisomerization. The effects are reversible by treatment with conventional chelating agents and brief heating, respectively. Accordingly, it is possible to trigger reactions that take place within a cylindrical capsule by light, even though the reaction process is not photochemical by nature. Likewise the presence of metals can regulate reactions without acting as direct catalysts. 相似文献
135.
An air-stable eight-coordinate (8C) Mn(II)N(8) complex has been synthesized utilizing an N(4) imidazole/imine ligand. The 8C dodecahedral geometry is structurally robust as the Mn complex is stable to air, NO(g), and potential coordinating anions. The structural, spectroscopic and water relaxivity properties of this complex are reported. 相似文献
136.
M. Sc. Edgar Uhl Dr. Peter Mayer Dr. Henry Dube 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(14):5779-5786
Light-driven molecular motors possess immense potential as central driving units for future nanotechnology. Integration into larger molecular setups and transduction of their mechanical motions represents the current frontier of research. Herein we report on an integrated molecular machine setup allowing the transmission of potential energy from a motor unit onto a remote receiving entity. The setup consists of a motor unit connected covalently to a distant and sterically encumbered biaryl receiver. By action of the motor unit, single-bond rotation of the receiver is strongly accelerated and forced to proceed unidirectionally. The transmitted potential energy is directly measured as the extent to which energy degeneration is lifted in the thermal atropisomerization of this biaryl. Energy degeneracy is reduced by more than 1.5 kcal mol−1, and rate accelerations of several orders of magnitude in terms of the rate constants are achieved. 相似文献
137.
138.
Henry Dube Dr. Besnik Kasumaj Carlos Calle Dr. Beatrice Felber Dr. Makoto Saito Dr. Gunnar Jeschke Prof. Dr. François Diederich Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(1):125-135
Distal hydrogen bonding in natural dioxygen binding proteins is crucial for the discrimination between different potential ligands such as O2 or CO. In the present study, we probe the chemical requirements for proper distal hydrogen bonding in a series of synthetic model compounds for dioxygen‐binding heme proteins. The model compounds 1‐Co to 7‐Co bear different distal residues. The hydrogen bonding in their corresponding dioxygen adducts is directly measured by pulse EPR spectroscopy. The geometrical requirements for this interaction to take place were found to be narrow and very specific. Only two model complexes, 1‐Co and 7‐Co , form a hydrogen bond to bound dioxygen, which was characterized in terms of geometry and nature of the bond. The geometry and dipolar nature of this interaction in 1‐Co ‐O2 is more similar to the one in natural cobalt myoglobin (Co‐Mb), making 1‐Co the best model compound in the entire series. 相似文献
139.
T. Dube 《Acta Mathematica Hungarica》2009,123(3):203-222
A point p of β, where X is a Tychonoff space, is called a remote point if for any nowhere dense D ⊆, X, p ∉ clβx
D. A subset S of X is called round if whenever the closure in βX of a zero-set of X contains S, then it is a neighborhood of S. The purpose of this paper is to study these notions in the pointfree context. In the process, we introduce N-homomorphisms
and show how the Stone extension of an N-homomorphism transfers remote points back and forth.
相似文献
140.
Enhancement of radiosensitivity of oral carcinoma cells by iodinated chlorin p6 copper complex in combination with synchrotron X‐ray radiation 下载免费PDF全文
The combination of synchrotron X‐ray radiation and metal‐based radiosensitizer is a novel form of photon activation therapy which offers the advantage of treating malignant tumors with greater efficacy and higher precision than conventional radiation therapy. In this study the anticancer cytotoxic efficacy of a new chlorophyll derivative, iodinated chlorin p6 copper complex (ICp6‐Cu), combined with synchrotron X‐ray radiation (8–10 keV) in two human oral cancer cell lines is explored. Pre‐treatment of cells with 20 µM and 30 µM ICp6‐Cu for 3 h was found to enhance the X‐ray‐induced cytotoxicity with sensitization enhancement ratios of 1.8 and 2.8, respectively. ICp6‐Cu localized in cytoplasm, mainly in lysosomes and endoplasmic reticulum, and did not cause any cytotoxicity alone. The radiosensitization effect of ICp6‐Cu accompanied a significant increase in the level of reactive oxygen species, damage to lysosomes, inhibition of repair of radiation‐induced DNA double‐strand breaks, increase in cell death and no significant effect on cell cycle progression. These results demonstrate that ICp6‐Cu is a potential agent for synchrotron photon activation therapy of cancer. 相似文献