Radical reaction of chlorophyll derivatives triggered by AIBN

Radical reactions of a C3-vinylated chlorophyll derivative, methyl pyropheophorbide-a, which were induced by thiols and the conventional initiator azobisisobutyronitrile (AIBN) were examined in vitro for the first time. Thiyl radicals attacked regioselectively at the sole C3-vinyl group, and the anti-Markovnikov sulfanyl adducts were obtained as major products. The other peripheral substituents, as well as the chlorin macrocycle, remained intact. The AIBN-induced radical reaction competed with co-oxidation that afforded the C3-formyl chlorin. This method can open new routes to derivatization of vinyl chlorins.     

Two-dimensional hydrophilic interaction chromatography coupling anion-exchange and hydrophilic interaction columns for separation of 2-pyridylamino derivatives of neutral and sialylated N-glycans

A novel chromatographic approach coupling anion-exchange (diethylaminoethylene) and hydrophilic-interaction (amide or zwitterionic type) columns was developed for the separating of 2-pyridylamino derivatives of N-glycans (PA-N-glycans). This is a kind of on-line, two-dimensional (2D) separation approach in hydrophilic-interaction chromatography (called the 2D-HILIC method), analogous to that of coupling cation- (or anion-, or mixed ion-) exchange and reversed-phase columns in hydrophobic interaction (reversed-phase) chromatography. The efficiency of the 2D-HILIC method was tested with biantennary neutral and sialylated PA-N-glycan standards by properly combining linear gradient elutions of water-acetonitrile and spiked-salt (ammonium acetate) elutions. The retention time RSDs of all the peaks in three sequential runs of a 100 min cycle are less than 0.52%, which indicates a reasonably good repeatability of the 2D-HILIC method. Then, the method was applied to a complex mixture of PA-N-glycans from human serum proteins. It was demonstrated that the neutral PA-N-glycans and mono-, di-, tri-, and tetrasialylated PA-N-glycans are able to be eluted in turn according to the number of sialic acids in an automated (programmed) single run.     

Separation and purification of isoflavones from Pueraria lobata by high-speed counter-current chromatography.

High-speed counter-current chromatography (HSCCC) was applied to the semipreparative separation and purification of puerarin and related isoflavones from a crude extract of Pueraria lobata. Analytical HSCCC was used for the preliminary selection of a suitable solvent system composed of ethyl acetate-n-butanol-water (2:1:3, v/v/v). Using the above solvent system the preparative HSCCC was successfully performed yielding six relatively pure isoflavones including puerarin from 80 mg of the crude extract in one-step separation.     

Rapid breakdown mechanisms of open air nanosecond dielectric barrier discharges

The discharge initiation mechanism of nanosecond dielectric barrier discharges in open air has been clarified with time-dependent measurement of the discharge electric field by electric-field-induced coherent Raman scattering and optical emission. Our experimental observations have revealed that, in the prebreakdown phase of a nanosecond dielectric barrier discharge, the externally applied fast-rising electric field is strongly enhanced near the cathode due to large accumulation of space charge, which then strongly enhances ionization near the cathode. Once a sufficiently large number of ionizations take place, the location of peak ionization forms a front and propagates toward the cathode with strong optical emission, which establishes the discharge. This process is essentially different from the well-known Townsend mechanism for slower discharges.     

Electrons and holes in HgTe and Hg0.82Cd0.18Te with controlled deviations from stoichiometry

The deviations from the stoichiometric composition of HgTe and Hg_0.82Cd_0.18Te crystals have been controlled by heat treatment under Hg vapor pressure. The magnetic field dependence of the Hall coefficient always shows the presence of two different sets of electrons and one set of holes. A low mobility electron is shown to belong to the conduction band. Vapor pressure dependence of hole concentration in HgTe shows that the concentration of nonstoichiometric defects decreases with increasing Hg vapor pressure, but the hole concentration is always higher than the electron concentration. In the case of Hg_0.82Cd_0.18Te, the electron concentration exceeds the hole concentration at high Hg vapor pressures. The dependence of the conduction band electron mobility in HgTe upon carrier density shows that the scattering by holes and impurities is predominant. In Hg_0.82Cd_0.18Te, however, optical phonon scattering is dominant when the deviation from stoichiometry is small and the effect of residual impurities can be neglected, and scattering by holes is dominant when the hole concentration is over $\text{10}{}^{17}\text{cm}{}^3$.     

Direct observation of dispersive Kondo resonance peaks in a heavy-fermion system

Ce 4d-4f resonant angle-resolved photoemission spectroscopy was carried out to study the electronic structure of strongly correlated Ce 4f electrons in a quasi-two-dimensional nonmagnetic heavy-fermion system CeCoGe1.2Si0.8. For the first time, dispersive coherent peaks of an f state crossing the Fermi level, the so-called Kondo resonance, are directly observed together with the hybridized conduction band. Moreover, the experimental band dispersion is quantitatively in good agreement with a simple hybridization-band picture based on the periodic Anderson model. The obtained physical quantities, i.e., coherent temperature, Kondo temperature, and mass enhancement, are comparable to the results of thermodynamic measurements. These results manifest an itinerant nature of Ce 4f electrons in heavy-fermion systems and clarify their microscopic hybridization mechanism.     

Structural-Deformation-Energy-Modulation Strategy in a Soft Porous Coordination Polymer with an Interpenetrated Framework

To achieve unique molecular-recognition patterns, a rational control of the flexibility of porous coordination polymers (PCPs) is highly sought, but it remains elusive. From a thermodynamic perspective, the competitive relationship between the structural deformation energy (E_def) of soft PCPs and the guest interaction is key for selective a guest-triggered structural-transformation behavior. Therefore, it is vital to investigate and control E_def to regulate this competition for flexibility control. Driven by these theoretical insights, we demonstrate an E_def-modulation strategy via encoding inter-framework hydrogen bonds into a soft PCP with an interpenetrated structure. As a proof of this concept, the enhanced E_def of PCP enables a selective gate-opening behavior toward CHCl₃ over CH₂Cl₂ by changing the adsorption-energy landscape of the compounds. This study provides a new direction for the design of functional soft porous materials.     

Interaction and arrangement of nitrogen and carbon atoms in fcc γ-iron

A Mössbauer effect measurement has been done for Fe?N, Fe?Al?C and Fe?Ni?C austenite in order to study the interaction between the interstitial atoms and their distribution among the octahedral sites of the fcc lattice, together with the influence of Al and Ni atoms. The spectra for Fe?N and Fe?Al?C austenite are decomposed into three components; one singlet γ₀, and two sets of doublet γ₁ and γ₂, with different quadrupole splittings, while no γ₂ component is found in the spectrum for Fe?Ni?C. By analyzing the component ratio in each spectrum, it is concluded that, in Fe?N and Fe?Al?C, the interaction between 2nd nearest neighboring nitrogen or carbon atoms is attractive, and is repulsive between 1st nearest for Fe?N, and that the interaction between 2nd nearest atoms is repulsive for Fe?Ni?C. By measuring the spectra of Fe?Ni?C in magnetic field, the sign of EFG for most of the γ₁ component is determined to be negative.     

Theoretical prediction for the ground state of (10 )H e with the method of analytic continuation in the coupling constant

Using the method of analytic continuation in the coupling constant with a (8)He +n+n model, we investigated the ground state of (10)He. In addition to a solution with the two valence neutrons in p states ( [ p(1/2 )p(1/2 )](0+ )), we obtained a solution with the valence neutrons in s states ( [s( 1/2) s(1/2)](0+) ) as the ground state. Experimentally, such a state has not yet been observed. This newly predicted state of (10)He with the main component of [s( 1/2)s (1/2) ](0+) corresponds to the ground state of (11)Li with a halo structure.