NH/pi interaction in a spin-crossover complex [FeII(HLMe)2](BPh4)2.2CH3CN (BPh4-=Tetraphenylborate; HLMe=2-Methylimidazol-4-yl-methylideneamino-2-ethylpyridine)

Three FeII complexes, [Fe(HLR)2](BPh4)2.solvent (R=H, Me, Ph), were synthesized, where BPh4-=tetraphenylborate and HLR=2-substituted-imidazol-4-yl-methylideneamino-2-ethylpyridine. The magnetic susceptibility measurements in 5-300 K revealed that [Fe(HLH)2](BPh4)2.H2O, [Fe(HLMe)2](BPh4)2.2CH3CN, and [Fe(HLPh)2](BPh4)2.CH3CN are low-spin (LS), spin-crossover (SC), and high-spin (HS) FeII complexes, respectively, indicating that the spin state can be effectively tuned by the bulkiness of the substituent. Complex shows a steep SC around 250 K, where it assumes a cyclic structure of {[Fe(HLMe)2]BPh4}2 constructed by four NH/pi bonds between the imidazole group and the phenyl ring of BPh4- in the HS state and a deformed structure with NH/pi bonds and linear CH3CN...HN hydrogen bonds at the terminals in the LS state.     

Identification of novel substituted fused aromatic compounds, meshimakobnol A and B, from natural Phellinus linteus fruit body

Novel 1H,6H-pyranyl[4,3-c][2]benzopyrane-1,6-diones, meshimakobnol A and B, were isolated from natural Phellinus linteus fruit body. The structure elucidation of these fused aromatic compounds was achieved by a spectroscopic method including the measurement of FG-HMBC with various delay times.     

Ru(η-1,3,5-cyclooctatriene)(η-dimethyl fumarate)2: a novel, versatile zerovalent ruthenium complex with electron-deficient olefinic ligands

The reactivity of a novel zerovalent ruthenium complex, Ru(η⁶-cot)(η²-dmfm)₂ (cot = 1,3,5-cyclooctatriene, dmfm, =dimethyl fumarate), which is readily prepared from Ru(η⁴-cod)(η⁶-cot) (cod = 1,5-cyclooctadiene) and dmfm was examined. The reaction with monodentate phosphine or amine ligands gave Ru(η⁶-cot)(dmfm)(L) (L = ligand) via dissociation of dmfm. Among bidentate phosphines, dppm (dppm = bis(diphenylphosphino)methane) reacted to give Ru(η⁴-cot)(dmfm)(dppm) along with releasing a dmfm ligand. In the case of dppe (dppe = 1,2-bis(diphenylphosphino)ethane), two types of complexes were obtained depending on the reaction conditions, Ru(dmfm)(dppe)₂ and an alkyl alkenyl complex; in the formation of the latter complex, sp² C-H bond activation of dmfm occurred. Ru(η⁴-cot)(dmfm)(N^?N) and Ru(dmfm)₂ (N^?N^?N) were formed by reacting with bidentate and tridentate nitrogen ligands. The reactions with arenes gave π-coordinated complexes, Ru(η⁶-arene)(dmfm)₂. p-Quinones and a p-biqunone reacted to give Ru(η⁶-cot)(p-quinone) and {Ru(η⁶-cot)}₂(p-biquinone), respectively, along with the dissociation of two dmfm ligands. It was found that low-valent ruthenium complexes preferably bear both electron-donating and accepting ligands simultaneously to be thermodynamically stable.     

A test of virtual vacuum polarizations in a strong electromagnetic field

A strong electromagnetic field may modify the refractive index of the normal vacuum, which can be reduced to the light-light scattering amplitude via virtual vacuum polarizations in a microscopic sense. In order to observe the increase of the refractive index, Cherenkov light emissions associated with relativistic electrons into the strong field can be utilized as an experimental probe. In this letter, we will present the results of an experimental search for Cherenkov emission with a laser intensity of 10¹⁷ W/cm² with a wavelength of 800 nm and an electron beam of 35.4 MeV/c, in which the expected Compton energy and indications of unexpected lower energies in the visible range were observed.     

Ultra-High Resolution Optical Coherence Tomography (OCT) Using a Halogen Lamp as the Light Source

The axial resolution of optical coherence tomography (OCT) is determined by the coherence length of the light source. We demonstrate for the first time high-resolution OCT of biological tissue using a halogen lamp as the light source for a low coherence interferometer. High-resolution OCT imaging with 3.5 μm resolution was performed successfully for onion and porcine skin, although the coherence light power for illumination of a sample is as small as 100 nW.     

Simultaneous Measurement of Refractive Index and Thickness of Transparent Plates by Low Coherence Interferometry

We demonstrate a novel low coherence Michelson interferometer which can provide simultaneous measurement of the refractive index and thickness of transparent plates used as a measured object. Unlike the existing low coherence interferometers reported so far, either an object or a focusing lens aligned on the signal arm is scanned repeatedly by a precise translation stage in synchronization with movement of a reflection mirror on the reference arm. The so-called object or lens scanning method gives us two measured quantities a movement distance of the stage between two light focusing states on the front and rear planes of an object and the corresponding optical path difference. These two measured quantities, result in desirable values of the index and thickness of the object with a short calculation. The measurement accuracy of ≤0.1% is expected for a thickness of more than 1 mm. In the experiment using the object scanning method, the accuracy of 0.3% or less was successfully attained for nearly 1-mm thick plates of fused quartz, sapphire, LiTaO₃ and slide glass.     

Chemical constituents from Sambucus adnata and their protein-tyrosine phosphatase 1B inhibitory activities

The MeOH extract from the whole plants of Sambucus adnata has shown significant protein-tyrosine phosphatase 1B (PTP1B) inhibitory activity. Chemical study on the extract resulted in the isolation of thirteen compounds, including a novel triterpene (1). The structure of 1 was determined to be 1α,3β-dihydroxy-urs-12-en-11-one-3-yl palmitate on the basis of extensive spectroscopic analyses. Among the isolated compounds, ursolic acid, oleanolic acid and (±)-boehmenan showed the most potent PTP1B inhibitory activity in vitro with the IC(50) values of 4.1, 14.4 and 43.5 μm, respectively. The kinetic analysis indicated that (±)-boehmenan inhibits PTP1B activity in a competitive manner.     

Rotamer-dependent chemiluminescence in the intramolecular charge-transfer-induced decomposition of bicyclic dioxetanes bearing a hydroxyaryl group

Base-induced chemiluminescent decomposition of acylamino-substituted dioxetane 1b bearing a 3-hydroxyphenyl group proceeded according to dual phase kinetics due to syn-anti isomerism of the aryl group. For dioxetane 7 bearing a 6-hydroxynaphthalen-2-yl group, syn- and anti-rotamers were each isolated and their structures were determined by X-ray single crystallographic analysis. Both rotamers underwent base-induced decomposition accompanied by the emission of red light to exclusively give the same keto imide 8. However, a marked difference in chemiluminescence efficiency was observed between anti-7 and syn-7.     

Photoelectrochemical evaluation of pH effect on hole transport through triplex-forming DNA immobilized on a gold electrode

We characterized pH effect on hole transport through DNA duplexes possessing a partial triplex-forming region. Direct electrochemical measurement of the current response of photosensitizer-tethered DNA immobilized on a gold electrode revealed that the partial triplex formation under acidic conditions suppressed photocurrent due to hole transport, while dissociation of the triplex into the duplex as occurred upon increasing pH values recovered the photocurrent efficiency. Reversible conversion between duplex and triplex induced upon cyclic alternation of pH values resulted in a rise and fall of photocurrent responses, indicating that pH change may feature in the switching function of hole transport in DNA. These electrochemical behaviors could be correlated to the results obtained in long-range photo-oxidative DNA cleavage experiments, in which DNA cleavage at the hole trapping site beyond the triplex region was significantly suppressed under triplex-forming acidic conditions.     

Color Formation and Gelation of Xyloglucan Upon Addition of Iodine Solutions

Summary: We developed a novel thermo‐reversible gelation system by mixing xyloglucan with an iodine solution. Xyloglucan dissolves in water to produce a colorless solution. However, the addition of iodine solution induces color and gelation; heating causes the gel to melt and become colorless. According to results from spectroscopic and small‐angle X‐ray scattering experiments, the gelation mechanism was proposed to involve two xyloglucan chains that associate side‐by‐side and incorporate iodine and/or iodide ions.

Xyloglucan gel prepared by mixing xyloglucan and iodine solution and heating to 60 °C, followed by cooling.