Spectroscopic fingerprints of valence and spin states in manganese oxides and fluorides

We performed a systematic study of soft X-ray absorption spectroscopy in various manganese oxides and fluorides. Both Mn L-edges and ligand (O and F) K-edges are presented and compared with each other. Despite the distinct crystal structure and covalent/ionic nature in different systems, the Mn-L spectra fingerprint the Mn valence and spin states through spectral lineshape and energy position consistently and evidently. The clear O- and F-K pre-edge features in our high resolution spectra enable a quantitative definition of the molecular orbital diagram with different Mn valence. In addition, while the binding energy difference of the O-1s core electrons leads to a small shift of the O-K leading edges between trivalent and quadrivalent manganese oxides, a significant edge shift, with an order of magnitude larger in energy, was found between divalent and trivalent compounds, which is attributed to the spin exchange stabilization of half-filled 3d system. This shift is much enhanced in the ionic fluoride system. This work provides the spectroscopic foundation for further studies of complicated Mn compounds.     

Reduced field-of-view diffusion-weighted imaging of the brain at 7 T

Ventral and rostral regions of the brain are of emerging importance for the MRI characterization of early dementia, traumatic brain injury and epilepsy. Unfortunately, standard single-shot echo planar diffusion-weighted imaging of these regions at high fields is contaminated by severe imaging artifacts in the vicinity of air–tissue interfaces. To mitigate these artifacts and improve visualization of the temporal and frontal lobes at 7 T, we applied a reduced field-of-view strategy, enabled by outer volume suppression (OVS) with novel quadratic phase radiofrequency (RF) pulses, combined with partial Fourier and parallel imaging methods. The new acquisition greatly reduced the level of artifacts in six human subjects (including four patients with early symptoms of dementia).     

Rovibrational and energetic analysis of the hydroxyethynyl anion (CCOH−)

For the first time, high-level structural and rovibrational data are provided for the hyroxyethynyl anion, CCOH^?. CCOH^? is a promising molecule for interstellar detection even though no new anions have been observed in the interstellar medium for the past half-decade. The large dipole moment of the corresponding neutral radical may be key for its creation as has been hypothesised and supported for other anions known to exist in various astronomical environments. Highly accurate quartic force fields are employed where previous benchmarks have produced spectroscopic constants and anharmonic vibrational frequencies within 20 MHz and 1 cm^?1, respectively, of experiment. This same approach is applied here for CCOH^? and its deuterated isotopologue with the goal of assisting laboratory experiments and/or astronomical observers in the potential detection of this anion.     

Facile Fabrication of Zirconia Modified Screen‐Printed Carbon Electrodes for Electrochemical Sensing of Phosphate

We report here a facile method to immobilize zirconia nanoparticles on a disposable screen‐printed carbon electrode (designated as ZrO₂‐SPCE) for phosphate sensor application. Simply by ultrasonicating a bare SPCE in a ZrO₂ slurry, ZrO₂ nanoparticles can be immobilized effectively on the electrode surface as verified by surface characterization evidences. Using ferricyanide as a redox probe, an increase in the charge transfer resistance (R_ct) of ferricyanide upon adsorption of phosphate on ZrO₂ is used for the determination of phosphate. This ZrO₂‐SPCE phosphate sensor shows a wide linear range up to 1 mM and a detection limit of 1.69 µM (S/N=3). Practical applicability of the ZrO₂‐SPCE is demonstrated by detecting phosphate content in human blood samples.     

Transfection of Mammalian Cells Using Block Copolypeptide Vesicles

An arginine‐leucine block copolypeptide (R₆₀L₂₀) is synthesized, which is capable of forming vesicles with controllable sizes, able to transport hydrophilic cargo across the cell membrane, and exhibit relatively low cytotoxicity. The R₆₀L₂₀ vesicles also possess the ability to deliver DNA into mammalian cells for transfection. Although the transfection efficiency is lower than that of the commercially available transfection agent Lipofectamine 2000, the R₆₀L₂₀ vesicles are able to achieve transfection with significantly lower cytotoxicity and immunogenicity. This behavior is potentially due to its stronger interaction with DNA which subsequently provides better protection against anionic heparin.

     

The Reduction of Aromatic Aldehydes and Benzils by Sodium Formaldehyde Sulphoxylate

Sodium formaldehyde sulphoxylate is shown to be an effective reagent for the reduction of some aromatic aldehydes to alcohols. Benzils are also reduced under neutral or basic conditions to give mainly benzoins. Ketones are reduced only slowly.     

Amidrazones 9. Convenient Syntheses of 1-Alkyl-1-Phenylhydrazines and α,β-Unsaturated Amidrazones Via Base-Promoted Reactions of 1,1-Disubstituted-3-Amino-4,5-Dihydro-1H-Pyrazolium Salts

A simple, efficient procedure for the conversion of phenylhydrazine to 1-alkyl-1-phenylhydrazines via base-promoted hydrolysis of 1-alkyl-3-amino-4,5-dihydro-1-phenyl-1H-pyrazolium iodides (2) is described. N¹, N¹-disubstituted hydrazones of trans-cinnamamide and acrylamide are obtained by Hofmann-type ring openings of 1,1 -disubstituted-3-amino-4,5-dihydro-5-phenyl (or 5-unsubstituted) -1H-pyrazolium halides (5, 7).     

An Oxidative Approach to a Hydroxypiperidinone Utilizing a Rh‐Catalyzed C‐H Activation Process

C‐H activation and isomerization using a Rh‐catalyst provided quick access to dehydropiperidine derivatives that could be further oxidized to hydroxypiperidinone derivatives.