Organic Chemistry Without Solvent. Improvements to the One Step Preparation of Dibenzyl Sulphones

Dibenzyl sulphones can be prepared from the corresponding benzyl halide under mild, economic and efficient conditions, using either sodium dithionite / Aliquat, or sodium formaldehyde sulphoxylate /potassium carbonate in the absence of solvent.     

A Convenient Procedure for the Hydrolysis of Hindered Esters

Although several procedures for the hydrolysis of hindered esters have been developed, most of them suffer from one or more disadvantages, either in lack of convenience or in stringent conditions which affect other functional groups. Among the presently available methods for effecting this conversion are lithium in ammonia, a strong reducing agent¹; boron trichloride, a Lewis acid²; and a variety of reagents which bring about alkyl-oxygen cleavage. Among the latter are lithium iodide in a variety of solvents, usually at elevated temperatures, or in the presence of an organic base³; 1,5-diazabicyclo [4, 3, 0] nonene-5, in boiling xylene⁴, a reaction which failed in this laboratory⁵; various mercaptides^6,7, which in addition to being experimentally offensive, also cleave aryl alkyl ethers.     

Focused ion beam preparation of samples for X‐ray nanotomography

The preparation of hard material samples with the necessary size and shape is critical to successful material analysis. X‐ray nanotomography requires that samples are sufficiently thin for X‐rays to pass through the sample during rotation for tomography. One method for producing samples that fit the criteria for X‐ray nanotomography is focused ion beam/scanning electron microscopy (FIB/SEM) which uses a focused beam of ions to selectively mill around a region of interest and then utilizes a micromanipulator to remove the milled‐out sample from the bulk material and mount it on a sample holder. In this article the process for preparing X‐ray nanotomography samples in multiple shapes and sizes is discussed. Additionally, solid‐oxide fuel cell anode samples prepared through the FIB/SEM technique underwent volume‐independence studies for multiple properties such as volume fraction, average particle size, tortuosity and contiguity to observe the characteristics of FIB/SEM samples in X‐ray nanotomography.     

High-performance aromatic polyimide fibers. 6. Structure and morphology changes in compressed BPDA-DMB fibers

A high-performance aromatic polyimide fiber has been spun from a high molecular weight polyimide synthesized from 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 2,2′-dimethyl-4,4′-diaminobiphenyl (DMB). The fiber exhibits not only excellent tensile properties and high temperature resistance but also a high compressive strength of 655 MPa. Morphological observations of BPDA-DMB fibers indicate that the fiber shows a skin-core structure and microfibrillar textures. A banded texture can also be found with a spacing of about 2μm, which may be introduced by the liquid crystalline behavior that appears during processing. Compressed BPDADMB fibers form kink and microkink bands over different size scales. The detailed formation mechanism of these banded textures is discussed. The structure parameter changes during compression-including crystal unit cell parameters, apparent crystallinity, crystal and overall orientation, and apparent crystallite sizes-are monitored. It is found that after restretching, the crystal and overall orientation is almost fully recovered while the apparent crystallinity is not recoverable. The structural changes during compression are critically associated with the loss of macroscopic mechanical property in the fibers.     

ThH5: An Actinide-Containing Superhalogen Molecule

Thorium and its compounds have been widely investigated as important nuclear materials. Previous research focused on the potential use of thorium hydrides, such as ThH₂, ThH₄, and Th₄H₁₅, as nuclear fuels. Here, we report studies of the anion, ThH₅⁻, by anion photoelectron spectroscopy and computations. The resulting experimental and theoretical vertical detachment energies (VDE) for ThH₅⁻ are 4.09 eV and 4.11 eV, respectively. These values and the agreement between theory and experiment facilitated the characterization of the structure of the ThH₅⁻ anion and showed its neutral counterpart, ThH₅ to be a superhalogen. ThH₅⁻, which exhibits a C_4v structure with five Th−H single bonds, possesses the largest known H/M ratio among the actinide elements, M. The adaptive natural density partitioning (AdNDP) method was used to further analyze the chemical bonding of ThH₅⁻ and to confirm the existence of five Th−H single bonds in the ThH₅⁻ molecular anion.     

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.