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171.
Four tetrameric nickel(II) pseudohalide complexes have been synthesized and structurally, spectroscopically, and magnetically characterized. Compounds 1-3 are isostructural and exhibit the general formula [Ni(2)(dpk·OH)(dpk·CH(3)O)(L)(H(2)O)](2)A(2)·2H(2)O, where dpk = di-2-pyridylketone; L = N(3)(-), and A = ClO(4)(-) for 1, L = NCO(-) and A = ClO(4)(-) for 2, and L = NCO(-) and A = NO(3)(-) for 3. The formula for 4 is [Ni(4)(dpk·OH)(3) (dpk·CH(3)O)(2)(NCO)](BF(4))(2)·3H(2)O. The ligands dpk·OH(-) and dpk·CH(3)O(-) result from solvolysis and ulterior deprotonation of dpk in water and methanol, respectively. The four tetramers exhibit a dicubane-like core with two missing vertexes where the Ni(II) ions are connected through end-on pseudohalide and oxo bridges. Magnetic measurements showed that compounds 1-4 are ferromagnetic. The values of the exchange constants were determined by means of a theoretical model based on three different types of coupling. Thus, the calculated J values (J(1) = J(2), J(3), and D) were 5.6, 11.8, and 5.6 cm(-1) for 1, 5.5, 12.0, and 5.6 cm(-1) for 2, 6.3, 4.9, and 6.2 cm(-1) for 3, and (J(1), J(2), J(3), and D) 6.9, 7.0, 15.2, and 4.8 cm(-1) for 4.  相似文献   
172.
As a part of systematic researches of phase transitions induced by shock compression in phosphates, silicates, germanates and sulfates, in this article we report preliminary results obtained from shock recovery experiments on powders of a gypsum mineral. The shock experiment was performed in a light gas gun until a pressure close to 14?GPa reached. The experimental techniques employed to analyze the shock effects on recovered samples were: Scanning Electron Microscopy (SEM), X-ray Powder Diffraction (XRD) and Micro-Raman Spectroscopy (MRS). The SEM observations show a high plasticity in the impacted sample composed mainly by gypsum and bassanite quantified by Rietveld analysis of the XRD. The results indicate the partial dehydration of gypsum as a result of impact. The MRS analysis suggests the presence of micro-mixtures of gypsum, bassanite and anhydrite heterogeneously distributed throughout the recovered sample.  相似文献   
173.
Using the Wald?s relation between the Noether charge of diffeomorphisms and the entropy for a generic spacetime possessing a bifurcation surface, we introduce a method to obtain a family of higher order derivatives effective actions from the entropy of black holes. We consider the entropy as the starting point and we analyze the procedure of derivation of the action functional. We specialize to a particular class of theories which simplifies the calculations, f(R) theories. We apply the procedure to loop quantum gravity and to a general class of log-corrected entropy formulas.  相似文献   
174.
Asymmetric telechelic α‐hydroxyl‐ω‐(carboxylic acid)‐poly(ε‐caprolactone) (HA‐PCL), α‐hydroxyl‐ω‐(benzylic ester)‐poly(ε‐caprolactone) (HBz‐PCL), and an asymmetric telechelic copolymer α‐hydroxyl‐ω‐(carboxylic acid)‐poly(ε‐caprolactone‐co‐γ‐butyrolactone) (HA‐PCB) were synthesized by ring‐opening polymerization of ε‐caprolactone (CL). CL and CL/γ‐butyrolactone mixture were used to obtain homopolymers and copolymer respectively at 150°C and 2 hr using ammonium decamolybdate (NH4) [Mo10O34] (Dec) as a catalyst. Water (HA‐PCL and HA‐PCB) or benzyl alcohol (HBz‐PCL) were used as initiators. The three polylactones reached initial molecular weights between 2000 and 3000 Da measured by proton nuclear magnetic resonance (1H‐NMR). Compression‐molded polylactone caplets were allowed to degrade in 0.5 M aqueous p‐toluenesulfonic acid at 37°C and monitored up to 60 days for weight loss behavior. Data showed that the copolymer degraded faster than the PCL homopolymers, and that there was no difference in the weight loss behavior between HA‐PCL and HBz‐PCL. Caplets of the three polylactones containing 1% (w/w) hydrocortisone were placed in two different buffer systems, pH 5.0 with citrate buffer and pH 7.4 with phosphate buffer at 37°C, and monitored up to 50 days for their release behavior. The release profiles of hydrocortisone presented two stages. The introduction of a second monomer in the polymer chain significantly increased the release rate, the degradation rate for HA‐PCB being faster than those for HBz‐PCL and HA‐PCL. At the pH studied, only slight differences on the liberation profiles were observed. SEM micrographs indicate that hydrolytic degradation occurred mainly by a surface erosion mechanism. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   
175.
The continually emerging functional significance of intrinsic disorder and conformational flexibility in proteins has challenged the long-standing dogma of a well-defined structure contributing to a specific function. Molten-globular states, a class of proteins with significant secondary-structure but a fluid hydrophobic core, is one such example. They have however been difficult to characterize due to the complexity of experimental data and lack of computational avenues. Here, we dissect the folding mechanism of the α-helical molten-globular protein NCBD from three fundamentally different approaches: statistical-mechanical variable barrier model, C(α)-based Gō-model and explicit water all-atom molecular dynamics (MD) simulations. We find that NCBD displays the characteristics of a one-state globally downhill folder but is significantly destabilized. Using simulation techniques, we generate a highly constrained but a heterogeneous native ensemble of the molten-globule for the first time that is consistent with experimental data including small angle X-ray scattering (SAXS), circular dichroism (CD), and nuclear magnetic resonance (NMR). The resulting native ensemble populates conformations reported in other bound-forms providing direct evidence to the mechanism of conformational selection for binding multiple partners in this domain. Importantly, our simulations reveal a connection between downhill folding and large conformational flexibility in this domain that has been evolutionarily selected and functionally exploited resulting in large binding promiscuity. Finally, the multimodel approach we employ here serves as a powerful methodology to study mechanisms and suggests that the thermodynamic features of molten-globules fall within the array of folding mechanisms available to small single-domain proteins.  相似文献   
176.
A route for the synthesis of hybrid materials using multiwalled carbon nanotubes (MWCNTS) and Cs3PMo12O40 was confirmed. The Cs3PMo12O40 salt was synthesized from H3PMo12O40·14H2O and CsCl. All compounds were characterized by Raman spectroscopy. The synthesis method can produce a chemically stable Cs3PMo12O40 molecule and pure and oxidized MWCNTS. Raman spectroscopy showed that the chemical interaction between MWCNTS and Cs3PMo12O40 was essentially of electrostatic nature. Raman spectra obtained with different wavelengths showed thermal decomposition of H3PMo12O40·14H2O (raw materials) from laser heating process. On the contrary, the synthesized compound (i.e. Cs3PMo12O40) was stable under the experimental conditions.  相似文献   
177.
Broadband UV-visible femtosecond transient absorption spectroscopy and steady-state integrated fluorescence were used to study the excited state dynamics of 7-dehydrocholesterol (provitamin D(3), DHC) in solution following excitation at 266 nm. The major results from these experiments are: (1) The excited state absorption spectrum is broad and structureless spanning the visible from 400 to 800 nm. (2) The state responsible for the excited state absorption is the initially excited state. Fluorescence from this state has a quantum yield of ~2.5 × 10(-4) in room temperature solution. (3) The decay of the excited state absorption is biexponential, with a fast component of ~0.4-0.65 ps and a slow component 1.0-1.8 ps depending on the solvent. The spectral profiles of the two components are similar, with the fast component redshifted with respect to the slow component. The relative amplitudes of the fast and slow components are influenced by the solvent. These data are discussed in the context of sequential and parallel models for the excited state internal conversion from the optically excited 1(1)B state. Although both models are possible, the more likely explanation is fast bifurcation between two excited state geometries leading to parallel decay channels. The relative yield of each conformation is dependent on details of the potential energy surface. Models for the temperature dependence of the excited state decay yield an intrinsic activation barrier of ~2 kJ/mol for internal conversion and ring opening. This model for the excited state behavior of DHC suggests new experiments to further understand the photochemistry and perhaps control the excited state pathways with optical pulse shaping.  相似文献   
178.
We study the black hole particle production in a regular spacetime metric obtained in a minisuperspace approach to loop quantum gravity. In different previous papers the static solution was obtained and shown to be singularity-free and self-dual. In this paper expanding a previous study of the black hole dynamics we repeat the Hawking analysis which leads to a thermal flux of particles at the future infinity. The evaporation time is infinite and the unitarity is recovered due to the regularity of the spacetime and to the characteristic behavior of the surface gravity.  相似文献   
179.
Francium combines a heavy nucleus (Z = 87) with the simple atomic structure of alkalis and is a very promising candidate for precision tests of fundamental symmetries such as atomic parity non-conservation measurements. Fr has no stable isotopes, and the ISAC radioactive beam facility at TRIUMF, equipped with an actinide target, promises to provide record quantities of Fr atoms, up to 1010/s for some isotopes. We discuss our plans for a Fr on-line laser trapping facility at ISAC and experiments with samples of cold Fr atoms. We outline our plans for a measurement of the nuclear anapole moment – a parity non-conserving, time-reversal conserving moment that arises from weak interactions between nucleons – in a chain of Fr isotopes. Its measurement is a unique probe for neutral weak interactions inside the nucleus.   相似文献   
180.
Edge polarization experiments were carried out on TJ-II using an electrode. It has been found that the plasma response is different at densities below and above the threshold value to trigger the spontaneously development of E × B sheared flows. At low densities, the edge plasma potential is fully controlled by external biasing, while at higher densities it is determined not only by external biasing but also by the electric fields spontaneous developed. Although an improvement in particle confinement is observed for both polarities, a larger increase is observed for negative electrode bias. Presented at the Workshop “Electric Fields, Structures and Relaxation in Edge Plasmas”, Tarragona, Spain, July 3–4, 2005.  相似文献   
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