Orbital ordering and magnetic field effect in MnV2O4

We studied the structural properties of an orbital-spin-coupled spinel oxide, MnV2O4, mainly by single-crystal x-ray diffraction measurement. It was found that a structural phase transition from cubic to tetragonal and ferrimagnetic ordering occur at the same temperature (Ts,TN=57 K). The structural phase transition was induced also by magnetic field above Ts. In addition, magnetic-field-induced alignment of tetragonal domains results in large magnetostriction below Ts. We also found that the structural phase transition is caused by the antiferro-type ordering of the V t2g orbitals.     

Magnitude and nature of interactions in benzene-X (X=ethylene and acetylene) in the gas phase: significantly different CH/pi interaction of acetylene as compared with those of ethylene and methane

The accurate interaction energies of the CH/pi interaction in the benzene-X clusters (X = ethylene and acetylene) were experimentally and theoretically determined. Two-color multiphoton ionization spectroscopy was applied, and the binding energies in the neutral ground state of the clusters were evaluated from the dissociation threshold measurements of the cluster cations. The experimental binding energies of the clusters (D0) were 1.4+/-0.2 and 2.7+/-0.2 kcal/mol, respectively. Estimated CCSD(T) interaction energies for the clusters at the basis set limit (De) were 2.2 and 2.8 kcal/mol, respectively. Calculated D0 values (1.7 and 2.4 kcal/mol, respectively) are close to the experimental values. Large electron correlation contributions (Ecorr=-3.6 and -2.8 kcal/mol, respectively) show that dispersion is the major source of the attraction in both clusters. The electrostatic interaction in the ethylene cluster is very small (-0.38 kcal/mol), as in the case of the benzene-methane cluster, whereas the electrostatic interaction in the acetylene cluster is large (-1.70 kcal/mol). The shifts of the S1-S0 transition also suggest that the ethylene cluster is a van der Waals-type cluster, but the acetylene cluster is a pi-hydrogen-bonded cluster. The nature of the CH/pi interaction of the "activated" alkyne C-H bond is significantly different from that of the "nonactivated" (or typical) alkane and alkene C-H bonds.     

Stepwise solvatochromism of ketyl anions in the gas phase: photodetachment excitation spectroscopy of benzophenone and acetophenone radical anions microsolvated with methanol

Electronic absorption spectra of bare and methanol-solvated radical anions of benzophenone ((C6H5)2CO) and acetophenone ((C6H5)CH3CO) were measured by monitoring the photodetachment efficiency in the gas phase. Strong absorption bands due to autodetachment after transitions to bound excited states were observed. Stepwise spectral shifts approaching the limit of the condensed phase spectra were found to occur as the cluster size increases. In the case of benzophenone radical anion, the solvation of two methanol molecules exhibits the near convergence to the limit, representing the full coordination with the solvent molecules around the carbonyl group. For the acetophenone case, the coordination number was not apparently determined because of their relatively small shifts. Relationships between hydrogen bonding and electronic structure are analyzed for the spectral shifts with the aid of calculations based on density functional theory. The calculational results show that the coordination angle of the solvent molecule is affected mostly by steric hindrance around the carbonyl group, and that there is no evidence for reorientation due to specific hydrogen bonding interaction with the singly occupied orbital, which has been formerly persisted for an interpretation of the transient absorption following pulse radiolysis in alcoholic solutions. An alternative possibility involving deformation with respect to intramolecular coordinates is discussed.     

A novel proton-selective sensor based on a sugar with hinge flexibility

A hinge sugar, a 2,4-diamino-2,4-dideoxy-beta-D-xylopyranoside derivative, turns its four equatorial substituents into axial orientations through a (4)C(1)-to-(1)C(4) ring flip in response to chelation to a metal ion. This hinge-like motion enables two components attached at the 1- and 3-positions to switch between far and near states. In this study, we examined the effect of N-alkylation on the bendability of the hinge molecule and synthesized a 2,4-dipyrenylmethyl derivative as a proton-selective sensor. (1)H NMR studies showed that N-alkylations of the hinge sugar facilitated (1)C(4) formation in the presence of an acid, probably because the increased basicity of the amino group promoted the intramolecular hydrogen bond between the 2- and 4-amino substituents, whereas chelation to a metal ion was hampered by the increased bulkiness. In accordance with the above results, N,N'-dipyrenylmethyl hinge sugar 3 emitted excimer fluorescence (445 nm) owing to the pyrene stacking as a result of the (1)C(4) formation at lower concentrations of trifuluoroacetic acid (TFA), while no significant changes in fluorescence spectra were observed when metal ions were added. Increase of the monomer fluorescence (375 nm) at higher TFA concentrations was also observed. These observations indicate that 3 could be used as a proton-selective sensor that covers a wide range of proton concentrations through monitoring of the two fluorescence maxima.     

Preparation of Mitochondria- and Epigenetics-Targeting Nanoparticles for Suppression of Cancer Metastasis

Epithelial-to-mesenchymal transition (EMT) of carcinoma cells is a promising target for cancer therapy since it is closely related to tumor metastasis and therapeutic resistance. The process of EMT is strongly associated with epigenetic alterations in cancer cells. In addition, recent accumulating evidence suggests that EMT also has a significant influence on inducing cancer stem cells (CSCs). In this study, novel polymer core–lipid shell nanoparticles (PLNPs) are prepared to suppress cancer EMT by the combined effects of the antioxidant activity of core-encapsulated Mn imidazolium porphyrin (MnImP) and the epigenetic control by histone acetyltransferase-encoding plasmid DNA (pHAT) hybridized onto the shell surface. PLNPs show the ability to control the expression of EMT-related markers, resulting in the suppression of EMT in lung epithelial cancer cells (paraquat-treated A549 cells). Furthermore, PLNPs suppress the levels of intracellular mitochondrial ROS and the transformation to CSCs. The results of this study may provide a novel therapeutic strategy against tumor metastasis and treatment resistance.     

Iron‐Catalyzed Chemoselective ortho Arylation of Aryl Imines by Directed C?H Bond Activation

No Fe‐ar : Iron catalyzes an imine‐directed C? H bond activation to introduce an ortho‐aryl group to an acetophenone‐derived imine using a diarylzinc reagent (see scheme), whereas palladium catalyzes the conventional substitution reaction . The title reaction features mild and selective C? H bond activation in the presence of aryl bromide, chloride, or sulfonate groups, and 1,2‐dichloroisobutane is essential to achieve such selectivity.

     

Characteristic velocity and dispersion relation of linear waves in extended thermodynamics of a van der Waals gas

We study the characteristic velocities of the extended thermodynamics of molecular rotational- and vibrational- relaxation processes for a van der Waals gas. The lower and upper bounds of the characteristic velocity are, respectively, estimated by the one of rarefied gases and the one evaluated on the spinodal curve. We also study the dispersion relation of linear waves, in particular, the phase velocity, attenuation factor and attenuation per wavelength in a low frequency region.