Gas-phase photoelectron spectroscopy and density functional theory have been used to investigate the electronic structures of open-shell bent vanadocene compounds with chelating dithiolate ligands, which are minimum molecular models of the active sites of pyranopterin Mo/W enzymes. The compounds Cp2V(dithiolate) [where dithiolate is 1,2-ethenedithiolate (S2C2H2) or 1,2-benzenedithiolate (bdt), and Cp is cyclopentadienyl] provide access to a 17-electron, d1 electron configuration at the metal center. Comparison with previously studied Cp2M(dithiolate) complexes, where M is Ti and Mo (respectively d0 and d2 electron configurations), allows evaluation of d0, d1, and d2 electronic configurations of the metal center that are analogues for the metal oxidation states present throughout the catalytic cycle of these enzymes. A "dithiolate-folding effect" that involves an interaction between the vanadium d orbitals and sulfur p orbitals is shown to stabilize the d1 metal center, allowing the d1 electron configuration and geometry to act as a low-energy electron pathway intermediate between the d0 and d2 electron configurations of the enzyme. 相似文献
We demonstrate the unique ability of catanionic vesicles, formed by mixing single-tailed cationic and anionic surfactants, to capture ionic solutes with remarkable efficiency. In an initial study (Wang, X.; Danoff, E. J.; Sinkov, N. A.; Lee, J.-H.; Raghavan, S. R.; English, D. S. Langmuir 2006, 22, 6461) with vesicles formed from cetyl trimethylammonium tosylate (CTAT) and sodium dodecylbenzenesulfonate (SDBS), we showed that CTAT-rich (cationic) vesicles could capture the anionic solute carboxyfluorescein with high efficiency (22%) and that the solute was retained by the vesicles for very long times (t1/2 = 84 days). Here we expand on these findings by investigating the interactions of both anionic and cationic solutes, including the chemotherapeutic agent doxorubicin, with both CTAT-rich and SDBS-rich vesicles. The ability of these vesicles to capture and hold dyes is extremely efficient (>20%) when the excess charge of the vesicle bilayer is opposite that of the solute (i.e., for anionic solutes in CTAT-rich vesicles and for cationic solutes in SDBS-rich vesicles). This charge-dependent effect is strong enough to enable the use of vesicles to selectively capture and separate an oppositely charged solute from a mixture of solutes. Our results suggest that catanionic surfactant vesicles could be useful for a variety of separation and drug delivery applications because of their unique properties and long-term stability. 相似文献
Three structurally different metallasiloxanes were formed from reactions between in situ generated suspensions of Ph2Si(OH)2/BuLi (1∶2) in tetrahydrofuran (THF) with, metal dichlorides MgCl2·2THF, CrCl2, or CoCl2 followed by toluene/Py (Py=pyridine) work-up. The X-ray structures are reported for: [Mg{O(Ph2SiO)2}2]-μ-(LiPy)-μ-{(LiPy)3(OH)(Cl)] (1) incorporating two six-membered magnesiasiloxane rings and an MgLi3O3Cl cubane fragment, [{O(Ph2SiO)2}Co{O(Ph2SiO)3}-μ-(LiPy2)2] (2) with both six-and eight-membered cobaltasiloxane rings and [Cr{O(Ph2SiO)2}2-μ-(LiPy2)2] (3) with two six-membered chromiasiloxane rings. Structure assembly in these cases is apparently dictated by the metal dichloride. The compound [{O(Ph2SiO)2}Mg{O(Ph2SiO)3}-μ-(CoClPy)2]·Py (4) is formed from [{O(Ph2SiO)2}Mg{O(Ph2SiO)3}-μ-(LiPy2)2] and CoCl2 (1∶2). 相似文献
The curing of a mesomorphic epoxy has been studied by polarized light microscopy (PLM) and differential scanning calorimetry. PLM in combination with wide‐angle X‐ray diffraction proves the formation of a liquid crystalline (LC) structure. An advanced isoconversional method reveals that the formation of the LC structure is accompanied by a dramatic decrease in the effective activation from ∼60 to ∼10 kJ · mol−1. A kinetic model of the phenomenon has been discussed.
The dependence of the activation energy on the extent of conversion for isothermal curing of the diglycidyl ether of 4,4′‐dihydroxybiphenyl/2,6‐diaminopyridine (diamonds) and DGEBA/2,6‐diaminopyridine (circles) systems. 相似文献
The specific role of the two cerebral hemispheres in processing idiomatic language is highly debated. While some studies show
the involvement of the left inferior frontal gyrus (LIFG), other data support the crucial role of right-hemispheric regions,
and particularly of the middle/superior temporal area. Time-course and neural bases of literal vs. idiomatic language processing
were compared. Fifteen volunteers silently read 360 idiomatic and literal Italian sentences and decided whether they were
semantically related or unrelated to a following target word, while their EEGs were recorded from 128 electrodes. Word length,
abstractness and frequency of use, sentence comprehensibility, familiarity and cloze probability were matched across classes. 相似文献