Flat corannulene: when a transition state becomes a stable molecule

Flat corannulene has been considered so far only as a transition state of the bowl-to-bowl inversion process. This study was driven by the prediction that substituents with strong steric repulsion could destabilize the bowl-shaped conformation of this molecule to such an extent that the highly unstable planar geometry would become an isolable molecule. To examine the substituents'' effect on the corannulene bowl depth, optimized structures for the highly-congested decakis(t-butylsulfido)corannulene were calculated. The computations, performed with both the M06-2X/def2-TZVP and the B3LYP/def2-TZVP methods (the latter with and without Grimme''s D3 dispersion correction), predict that this molecule can achieve two minimum structures: a flat carbon framework and a bowl-shaped structure, which are very close in energy. This rather unusual compound was easily synthesized from decachlorocorannulene under mild reaction conditions, and X-ray crystallographic studies gave similar results to the theoretical predictions. This compound crystallized in two different polymorphs, one exhibiting a completely flat corannulene core and the other having a bowl-shaped conformation.

The first flat metal-free corannulene derivative was predicted by computations and achieved by synthesis.     

Advantages of mesh tallying in MCNP5 for soil analysis calculations

The Monte Carlo code, MCNP5, includes a mesh and lattice tally option useful for large matrix calculations. Recently, a fast lattice tally (FLT) was developed for MCNPX. We used these two codes to model an in-situ soil analysis system based on inelastic neutron scattering. The tallies were utilized to calculate the reaction rates of fast neutrons with carbon via inelastic reactions. The results of these three tallies and their respective computational times are compared, and the advantages of these methodologies discussed.     

Self-immolative polymers

Smart polymers are special kinds of polymeric molecules that respond to external stimuli. We have developed a novel smart polymer designed to sequentially disassemble into its building blocks upon initiation by a triggering event at the polymer head. The polymer structure is based on a polyurethane backbone that disassembles through a domino-like, 1,6-elimination and decarboxylation reactions. We synthesized a self-immolative polymer that amplifies a single cleavage reaction into multiple release of fluorogenic molecules and confirmed the head-to-tail disassembly concept. These polymers can be used to prepare highly sensitive molecular sensors with large signal-to-noise ratios. The sensors should be useful for the detection of a wide range of biological and chemical activities through use of the appropriate trigger at the polymer head.     

A brief review: Past,present and future of lithium ion batteries

The review summarizes the development of lithium ion batteries beginning with the research of the 1970–1980s which lead to modern intercalation type batteries. Following the history of lithium ion batteries, material developments are outlined with a look at cathode materials, electrolyte solutions and anode materials. Finally, with lithium sulfur and lithium oxygen batteries two post intercalation type lithium batteries are discussed. The focus of the material discussions lies on basic understanding, problems and opportunities related to the materials.     

Is it True That the Normal Valence‐Length Correlation Is Irrelevant for Metal–Metal Bonds?

The most intriguing feature of metal–metal bonds in inorganic compounds is an apparent lack of correlation between the bond order and the bond length. In this study, we combine a variety of literature data obtained by quantum chemistry and our results based on the empirical bond valence model (BVM), to confirm for the first time the existence of a normal exponential correlation between the effective bond order (EBO) and the length of the metal–metal bonds. The difference between the EBO and the formal bond order is attributed to steric conflict between the (TM)_n cluster (TM=transition metal) and its environment. This conflict, affected mainly by structural type, should cause high lattice strains, but electron redistribution around TM atoms, evident from the BVM calculations, results in a full or partial strain relaxation.     

Miniature array postdetection-encoded MRI

A method for performing nuclear magnetic resonance (NMR) measurements simultaneously from more than a single radiofrequency (RF) coil is presented. The method employs the detection of magnetic resonance signals in an array of detectors, where each detector is responsible for detecting a unique frequency bandwidth or a magnetic resonance signal from a unique location in a region in a primary, substantially homogeneous, static magnetic field. The detectors may be separated logically into groups, whereby all the detectors in a given group are essentially RF-decoupled from each other to substantially eliminate cross-talk by switching circuits or by being placed from each other sufficiently remotely. Sampling of detected signals from detectors in this array is done simultaneously over groups of noninteracting detectors. The detected signals from all detectors in a given group are simultaneously transmitted to a single preamplifier, thus increasing significantly the signal-to-noise ratio (SNR) in that preamplifier. Prior to transmitting each detected NMR signal of each detector to the preamplifier, each detected signal is separately and uniquely encoded electronically. This provides a method whereby the signal of each detector is uniquely encoded. Accumulating all these encoded signals, which were simultaneously received in a number of RF detectors into a single amplifier, results in the total signal having a high SNR ratio. This total amplified signal is later decoded into each detector's original signal by a decoding circuitry. Conventional magnetic resonance imaging (MRI) techniques may be thereafter applied to obtain an image. Or else, conventional NMR techniques may be thereafter applied to obtain an improved SNR from a sample, using a single preamplifier with a multitude of detectors. Applying this method to a large number of miniature and closely packed RF detectors placed in an array-like configuration results in an MRI technique with a very fast acquisition time, an increased SNR and a high spatial resolution equivalent to the number of detectors per unit of length. Deblurring and decoupling algorithms allow for images from layers as deep as 6 mm to be acquired.     

Effect of sonochemistry: Li- and Mn-rich layered high specific capacity cathode materials for Li-ion batteries

Li- and Mn-rich layered Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ cathode material was synthesized using sonochemical method followed by annealing at 700, 800, and 900 °C for 10 h. The material was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), Raman spectroscopy, and electrochemical techniques. Its performance as a cathode material for Li-ion batteries was examined. With the sample annealed at 900 °C, an initial specific capacity of 240 mAh g^?1 was obtained, which decreased to 215 mAh g^?1 after 80 cycles, thus retaining about 90 % of its initial capacity. In contrast, samples annealed at lower temperatures exhibited lower capacity retention upon cycling. Thus, the final annealing temperature was found to have a significant effect on the electrochemical stability of this material in terms of capacity, average voltage, and rate capability. The advantage of this synthesis, which includes a sonochemical stage, compared with a conventional co-precipitation synthesis, was also confirmed.