Oxidations of hydrocarbons by manganese(III) tris(hexafluoroacetylacetonate)

Mn(hfacac)(3) is an easily prepared and reactive oxidant (hfacac = hexafluoroacetylacetonate). It forms stable solutions in benzene and methylene chloride but is rapidly reduced in acetonitrile, DMSO, acetone, and ethers. It is reduced by ferrocene to give the Mn(II) complex [Cp(2)Fe][Mn(hfacac)(3)], which has been structurally characterized. Mn(hfacac)(3) also rapidly oxidizes 1-acetylferrocene, 1,1'-diacetylferrocene, and tris(4-bromophenyl)amine. Based on an equilibrium established with tris(2,4-dibromophenyl)amine, a redox potential of 0.9 +/- 0.1 V vs Cp(2)Fe(+/0) is calculated. Mn(hfacac)(3) oxidizes 9,10-dihydroanthracene (DHA) cleanly to anthracene, with a bimolecular rate constant of 6.8 x 10(-4) M(-1) s(-1) at 25 degrees C in benzene solution. In the presence of small amounts of water, the manganese(II) product is isolated as cis-Mn(hfacac)(2)(H(2)O)(2), which has also been structurally characterized. Mn(hfacac)(3) also oxidizes xanthene to 9,9'-bixanthene, 1,4-cyclohexadiene to benzene, and 2,4-di-tert-butylphenol to the phenol dimer. Toluene and substituted toluenes are oxidized to tolylphenylmethanes. Product analyses and relative rates--for instance that p-methoxytoluene reacts much faster than toluene--indicate that the more electron rich substrates react by initial electron transfer to manganese. For the less electron rich substrates, such as 1,4-cyclohexadiene, a mechanism of initial hydrogen atom transfer to Mn(hfacac)(3) is suggested. The ability of Mn(hfacac)(3) to abstract H* is reasonable given its high redox potential and the basicity of [Mn(hfacac)(3)](-). In CH(2)Cl(2) solution, oxidation of DHA is catalyzed by chloride ion.     

Multivalent, bifunctional dendrimers prepared by click chemistry

Unsymmetrical dendrimers, containing both mannose binding units and coumarin fluorescent units, have been prepared using click chemistry and shown to be highly efficient, dual-purpose recognition/detection agents for the inhibition of hemagglutination.     

Interstitial and substitutional light elements in transition metals for heterogeneous catalysis

The addition of foreign element dopants to monometallic nanoparticle catalysts is of great importance in industrial applications. Both substitutional and interstitial doping of pure metallic phases can give profound effects such as altering electronic and transport properties, lattice parameters, phase transitions, and consequently various physicochemical properties. For transition metal catalysts, this often leads to changes in catalytic activity and selectivity. This article provides an overview of the recent developments regarding the catalytic properties and characterisation of such systems. In particular, the structure–activity relationship for a number of important chemical reactions is summarised and the future prospects of this area are also explored.

TOC summarises some recent developments in synthesis, characterisation and catalytic applications of light elements doped to transition metals presented in this article.     

Excitation ratiometric chloride sensing in a standalone yellow fluorescent protein is powered by the interplay between proton transfer and conformational reorganization

Natural and laboratory-guided evolution has created a rich diversity of fluorescent protein (FP)-based sensors for chloride (Cl⁻). To date, such sensors have been limited to the Aequorea victoria green fluorescent protein (avGFP) family, and fusions with other FPs have unlocked ratiometric imaging applications. Recently, we identified the yellow fluorescent protein from jellyfish Phialidium sp. (phiYFP) as a fluorescent turn-on, self-ratiometric Cl⁻ sensor. To elucidate its working mechanism as a rare example of a single FP with this capability, we tracked the excited-state dynamics of phiYFP using femtosecond transient absorption (fs-TA) spectroscopy and target analysis. The photoexcited neutral chromophore undergoes bifurcated pathways with the twisting-motion-induced nonradiative decay and barrierless excited-state proton transfer. The latter pathway yields a weakly fluorescent anionic intermediate , followed by the formation of a red-shifted fluorescent state that enables the ratiometric response on the tens of picoseconds timescale. The redshift results from the optimized π–π stacking between chromophore Y66 and nearby Y203, an ultrafast molecular event. The anion binding leads to an increase of the chromophore pK_a and ESPT population, and the hindrance of conversion. The interplay between these two effects determines the turn-on fluorescence response to halides such as Cl⁻ but turn-off response to other anions such as nitrate as governed by different binding affinities. These deep mechanistic insights lay the foundation for guiding the targeted engineering of phiYFP and its derivatives for ratiometric imaging of cellular chloride with high selectivity.

We discovered an interplay between proton transfer and conformational reorganization that powers a standalone fluorescent-protein-based excitation-ratiometric biosensor for chloride imaging.     

Dinuclear cobalt bis(dioxolene) complex exhibiting two sequential thermally induced valence tautomeric transitions

4,6-Di-2'-pyridylpyrimidine is employed as a bis(diimine) ligand bridging two cobalt bis(dioxolene) centers. The thermally induced valence tautomeric transitions of these two metal centers are coupled through the ligand. The result is that sequential switching from high-spin Co(II) to low-spin Co(III) of one center, followed by the onset of switching of the other center at lower temperature, is observed in a solid amorphous thin film by IR absorption spectroscopy.     

High-resolution gadolinium-enhanced 3D MRA of the infrapopliteal arteries. Lessons for improving bolus-chase peripheral MRA

Peripheral magnetic resonance angiography (MRA) is growing in use. However, methods of performing peripheral MRA vary widely and continue to be optimized, especially for improvement in illustration of infrapopliteal arteries. The main purpose of this project was to identify imaging factors that can improve arterial visualization in the lower leg using bolus chase peripheral MRA. Eighteen healthy adults were imaged on a 1.5T MR scanner. The calf was imaged using conventional three-station bolus chase three-dimensional (3D) MRA, two dimensional (2D) time-of-flight (TOF) MRA and single-station Gadolinium (Gd)-enhanced 3D MRA. Observer comparisons of vessel visualization, signal to noise ratios (SNR), contrast to noise ratios (CNR) and spatial resolution comparisons were performed. Arterial SNR and CNR were similar for all three techniques. However, arterial visualization was dramatically improved on dedicated, arterial-phase Gd-enhanced 3D MRA compared with the multi-station bolus chase MRA and 2D TOF MRA. This improvement was related to optimization of Gd-enhanced 3D MRA parameters (fast injection rate of 2 mL/sec, high spatial resolution imaging, the use of dedicated phased array coils, elliptical centric k-space sampling and accurate arterial phase timing for image acquisition). The visualization of the infrapopliteal arteries can be substantially improved in bolus chase peripheral MRA if voxel size, contrast delivery, and central k-space data acquisition for arterial enhancement are optimized. Improvements in peripheral MRA should be directed at these parameters.     

Endoepitaxial growth of hexagonal-Fe13Ge8 islands on Cubic-Ge(001)

The growth and shape evolution of epitaxial Fe₁₃Ge₈ (hexagonal lattice) islands on single crystal Ge(001) (cubic lattice) substrate was observed in real time using an in situ ultra-high vacuum transmission electron microscope (TEM). Post-deposition high-resolution TEM in conjunction with stereographic projection enabled the identification of the interface structure between the Fe₁₃Ge₈ islands and the Ge substrate. Only one low-energy coherent interface formed via Fe₁₃Ge₈ islands growing into the substrate along the inclined Ge(11?1) plane. This indicates that minimization of net interfacial energy is the driving force for hexagonal Fe₁₃Ge₈ islands formation on Ge(001).     

Grain growth process of two-phase nanocrystalline soft magnetic materials

In order to clarify the origin of the high thermal stability of the microstructure in bcc-Fe/amorphous two-phase nanocrystalline soft magnetic materials, we have investigated the changes in the magnetic and microstructural properties upon isothermal annealing at 898 K for an Fe₈₉Zr₇B₃Cu₁ alloy by means of transmission electron microscopy, Mössbauer spectroscopy and DC magnetometry. The mean grain size was found to remain almost unchanged at the early stage of annealing. However, rapid grain coarsening was evident at an annealing time of 7.2 ks where the intergranular amorphous phase begins to crystallize into Fe₂₃Zr₆. The grain growth process with a kinetic exponent of 1.6 is observed for the growth process beyond this annealing time, reflecting the disappearance of the intergranular amorphous phase. Our results confirm that the thermal stability of the bcc-Fe/amorphous two-phase nanocrystalline soft magnetic alloys is governed by the residual amorphous phase.     

Characteristics of driven polymer surfaces: growth and roughness

Using a Monte Carlo simulation, the growth and roughness characteristics of polymer surfaces are studied in 2+1 dimensions. Kink-jump and reptation dynamics are used to move polymer chains under a driving field where they deposit onto an impenetrable attractive wall. Effects of field (E), chain length (L(c)), and the substrate size (L) on the growing surfaces are studied. In low field, the interface width (W) shows a crossover from one power-law growth in time (W approximately t(beta(1))) to another (W approximately t(beta(2))), before reaching its asymptotic value (W(s)), with beta(1)( approximately 0.5+/-0.1)相似文献   

Photonic microring resonator modulated resonance response analysis

This paper presents the resonance response analysis of a photonic microring resonator. It covers the mathematical as well as simulation analysis on the modulated signals. The mathematical formulation provides a relation of several microring resonator parameters that could potentially affect the ring resonator performances. The simulation shows a graphical representation of the ring resonator full-width at half-max, quality factor (Q-factor) as well as the depth of the resonance at different modulation voltages applied to the ring. Several parameters have also been altered which is the ring radius, the coupling coefficient of the waveguides as well as the waveguide material group index. With this investigation, we determine the possible cause of the change in Q factor of a silicon microring resonator when the resonance is modulated and the possible solution to minimize the problem.