Solvent effects on oxygen atom transfer reaction between manganese(V)-oxo corrole and alkene

Pseudo-first order reaction rate constants of 5,10,15-tris（pentafluorophenyl）corrole Mn（V）-oxo (F₁₅CMn（V）-oxo),5,15-bis（pentafluorophenyl）-10-（phenyl）corrole Mn（V）-oxo(F₁₀CMn（V）-oxo),5,15- bis（phenyl）-10-（pentafluorophenyl）corrole Mn（V）-oxo（F₅CMn（V）-oxo） and 5,10,15-tris（phenyl）corrole Mn（V）-oxo（F₀CMn（V）-oxo） with a series of alkene substrates in different solvents were determined by UV-vis spectroscopy.The results indicated that the oxygen atom transfer pathway between Mn（V）-oxo corrole and alkene is solvent-dependent.     

DTI at 7 and 3 T: systematic comparison of SNR and its influence on quantitative metrics

Diffusion tensor imaging (DTI) and advanced related methods such as diffusion spectrum and kurtosis imaging are limited by low signal-to-noise ratio (SNR) at conventional field strengths. DTI at 7 T can provide increased SNR; however, B0 and B1 inhomogeneity and shorter T2? still pose formidable challenges. The purpose of this study was to quantify and compare SNR at 7 and 3 T for different parallel imaging reduction factors, R, and TE, and to evaluate SNRs influences on fractional anisotropy (FA) and apparent diffusion coefficient (ADC). We found that R>4 at 7 T and R≥2 at 3 T were needed to reduce geometric distortions due to B0 inhomogeneity. For these R at 7 T, SNR was 70-90 for b=0 s/mm² and 22-28 for b=1000s/mm² in central brain regions. SNR was lower at 3 T (40 for b=0 s/mm² and 15 for b=1000 s/mm²) and in lateral brain regions at 7 T due to B1 inhomogeneity. FA and ADC did not change with MRI field strength, SENSE factor or TE in the tested range. However, the coefficient of variation for FA increased for SNR <15 and for SNR <10 in ADC, consistent with published theoretical studies. Our study demonstrates that 7 T is advantageous for DTI and lays the groundwork for further development. Foremost, future work should further address challenges with B0 and B1 inhomogeneity to take full advantage for the increased SNR at 7 T.     

β-Octafluorinated tetrakis(ethoxycarbonyl)porphyrin

Tetrakis(alloxycarbonyl)porphyrin and its β-octafluoro-substituted derivatives were synthesized via Lindsey method and transformed to their zinc complexes.Single crystal X-ray structures of corresponding Zn(Ⅱ) porphyrins revealed that β-octafluorination will give more compactness of porphyrin moieties in the crystal structure owing to the hydrogen bonding interactions involving β-fluorine atoms.An unusual six-coordinated Zn(Ⅱ) was found via intramolecular coordination of oxygen atom of meso-substituents with central Zn(Ⅱ).     

DSC examination of the rotator cuff muscles in rabbits

Rotator cuff tear is a common musculoskeletal disorder with pathological changes occurring in the structure of the rotator cuff musculature (fatty infiltration). Severe fatty infiltration, observed on MRI or CT scan, negatively influences the result of rotator cuff reconstruction in human beings. The basic histological and biochemical alterations in fatty infiltration of the rotator cuff muscle with torn tendon are still not clear. Differential scanning calorimetric (DSC) examination is a well-established method for the demonstration of thermal consequences of local and global conformational changes in biological systems. With foregoing studies, authors have demonstrated the feasibility of DSC in the investigation of the musculoskeletal system. The aim of this study was to establish the thermograms of the rotator cuff muscles with normal and torn tendons, experimentally induced in rabbits. The DSC results clearly proved that definitive differences are present between the muscles with normal and torn tendons, which have also been demonstrated by MRI and CT scans.     

Efficient Synthesis of Cryptophycin‐52 and Novel para‐Alkoxymethyl Unit A Analogues

Cryptophycins are a family of highly cytotoxic, cyclic depsipeptides. They display antitumour activity that is largely maintained for multi‐drug‐resistant tumour cells. Cryptophycins are composed of four building blocks (units A–D) that correspond to the respective amino and hydroxy acids. A new synthetic route to unit A allows the selective generation of all four stereogenic centres in a short, efficient and reliable synthesis and contributes to an easier and faster synthesis of cryptophycins. The first two stereogenic centres are introduced by a catalytic asymmetric dihydroxylation, whereas the remaining two stereogenic centres are introduced with substrate control of diastereoselectivity. The stereogenic diol function also serves as the epoxide precursor. The approach was used to synthesise the native unit A building block as well as three para‐alkoxymethyl analogues from which cryptophycin‐52 and three analogous cryptophycins were prepared. Macrocyclisation of the seco‐depsipeptides was based on ring‐closing metathesis.     

Coverage-dependent adsorption geometry of octithiophene on Au(111)

The adsorption behavior of α-octithiophene (8T) on the Au(111) surface as a function of 8T coverage has been studied with low-temperature scanning tunneling microscopy, high resolution electron energy loss spectroscopy as well as with angle-resolved two-photon photoemission and ultraviolet photoemission spectroscopy. In the sub-monolayer regime 8T adopts a flat-lying adsorption geometry. Upon reaching the monolayer coverage the orientation of 8T molecules changes towards a tilted configuration, with the long molecular axis parallel to the surface plane, facilitating attractive intermolecular π-π-interactions. The photoemission intensity from the highest occupied molecular orbitals (HOMO and HOMO - 1) possesses a strong dependence on the adsorption geometry due to the direction of the involved transition dipole moment for the respective photoemission process. The change in molecular orientation as a function of coverage in the first molecular layer mirrors the delicate balance between intermolecular and molecule/substrate interactions. Fine tuning of these interactions opens up the possibility to control the molecular structure and accordingly the desirable functionality.     

High field Mössbauer investigations of FexN (x=3,4)

⁵⁷Fe transmission Mössbauer measurements were carried out on Fe₃N and Fe₄N in applied fields up to 13.5 T to study the influence of an external field (B _a) on the hyperfine field of Fe atoms with localized and itinerant moments. These results are compared with augmented spherical wave band structure calculations.     

Novel Experimental Technique for the Determination of Monomer Droplet Size Distribution in Miniemulsion

Summary: The lack of accurate knowledge for measuring monomer droplet size and droplet size distribution has hampered the further progress of miniemulsion polymerization. Monomer droplet size is probably the most important characteristics of a miniemulsion, influencing the miniemulsion stability and the nucleation mechanism. To date, several experimental techniques have been tested to measure miniemulsion droplet size, but none are convenient and accurate. This work presents a novel experimental technique, using a powerful new scanning transmission electron microscopy (STEM) imaging system, which allows transmission observations of wet samples in an environmental scanning electron microscopy (ESEM). This new imaging technique is a useful technique to directly measure droplet size and droplet size distribution.

Miniemulsion droplets in dark field wet STEM imaging conditions.