Ultraviolet-A irradiation to the eye modulates intestinal mucosal functions and properties of mast cells in the mouse

We previously reported that topical irradiation of the eye by ultraviolet-B (UVB) activated hypothalamo-pituitary-adrenal axis (HPA-A) of the mouse to increase 3, 4-dihydroxyphenylalanine (DOPA)-positive melanocytes in the skin by an inducible nitric oxide synthase (iNOS)-dependent mechanism. This work demonstrates that irradiation of the eye by ultraviolet-A (UVA) specifically increased DOPA-positive cells in the mucosa of the jejunum and colon of C57BL/6J mice by some HPA- and iNOS-independent mechanism. UVA-induced increase in DOPA-positive cells in the intestine was inhibited by the administration of hexamethonium or prazosin plus propranolol, blockers for the sympathetic nervous system. UVA irradiation of the eye increased DOPA- and histidine decarboxylase (HDC)-positive cells in the intestinal mucosa of both C57BL/6J and WBB6F1/J mice but not in the mutant strain W/Wv of the latter that lack mast cells. UVA irradiation of the eye suppressed the intestinal peristalsis of control, hypophysectomized or iNOS(-/-) C57BL/6J mice by the mechanism that was inhibited by hexamethonium or prazosin plus propranolol. These observations suggest that UVA irradiation of the eye stimulated the sympathetic nervous system to increase the mucosal DOPA- and HDC-positive mast cells and suppressed the peristalsis of the small intestine of the mouse.     

Cyanide-bridged [Fe8M6] clusters displaying single-molecule magnetism (M=Ni) and electron-transfer-coupled spin transitions (M=Co)

Cyanide‐bridged metal complexes of [Fe₈M₆(μ‐CN)₁₄(CN)₁₀ (tp)₈(HL)₁₀(CH₃CN)₂][PF₆]₄?n CH₃CN?m H₂O (HL=3‐(2‐pyridyl)‐5‐[4‐(diphenylamino)phenyl]‐1H‐pyrazole), tp^?=hydrotris(pyrazolylborate), 1 : M=Ni with n=11 and m=7, and 2 : M=Co with n=14 and m=5) were prepared. Complexes 1 and 2 are isomorphous, and crystallized in the monoclinic space group P2₁/n. They have tetradecanuclear cores composed of eight low‐spin (LS) Fe^III and six high‐spin (HS) M^II ions (M=Ni and Co), all of which are bridged by cyanide ions, to form a crown‐like core structure. Magnetic susceptibility measurements revealed that intramolecular ferro‐ and antiferromagnetic interactions are operative in 1 and in a fresh sample of 2 , respectively. Ac magnetic susceptibility measurements of 1 showed frequency‐dependent in‐ and out‐of‐phase signals, characteristic of single‐molecule magnetism (SMM), while desolvated samples of 2 showed thermal‐ and photoinduced intramolecular electron‐transfer‐coupled spin transition (ETCST) between the [(LS‐Fe^II)₃(LS‐Fe^III)₅(HS‐Co^II)₃(LS‐Co^III)₃] and the [(LS‐Fe^III)₈(HS‐Co^II)₆] states.     

Electronic structure analysis of iron(III)-porphyrin complexes by X-ray absorption spectra at the C, N and Fe K-edges.

X-ray absorption near edge structure (XANES) measurements at the C, N, and Fe K absorption edges were performed for iron(III)-tetraphenylporphyrin (FeTPP), iron(III)-tetrakis(p-carboxyphenyl)porphyrin (FeTCPP), and iron(III)-tetrakis(p-sulfonatophenyl)porphyrin (FeTSPP). The spectral shapes differ in the Fe K XANES, but not in C and N K XANES among FeTPP, FeTCPP, and FeTSPP. Crosschecks of XANES data for C, N, and Fe K absorption edges in combination with discrete variational (DV)-Xalpha molecular orbital (MO) calculations indicate that each p-electron-withdrawing group on four meso-phenyl substitutes in an Fe(III)-porphyrin complex brings about a unique electron state through the complex because of the electron-withdrawal strength, itself. Consequently, they affect the positive charge of the center Fe(III) ion.     

Local structure of nitrogen atoms in a porphine ring of mesophenyl substituted porphyrin with an electron-withdrawing group using X-ray photoelectron spectroscopy and X-ray absorption spectroscopy.

This study investigated the protonation of nitrogen atoms in porphyrins with meso-phenyl p-substituted by an electron-withdrawing group using N 1s X-ray photoelectron spectroscopy (XPS), the N K X-ray absorption near-edge structure (XANES), and the discrete variational (DV)-Xalpha molecular orbital (MO) method. Both tetraphenylporphyrin (TPP) and tetrakis(p-sulfonatophenyl)porphyrin (TSPP) have a single structure: the former has two protonated and two non-protonated N atoms in the porphine ring; the latter has four protonated N atoms in the porphine ring. In contrast, a combination of XPS, XANES, and DV-Xalpha MO calculations shows that tetrakis(p-carboxyphenyl)porphyrin (TCPP) has a dual structure: one structure has two protonated and two non-protonated N atoms; the other has four protonated N atoms. Furthermore, this result was also considered based on the protonation constants of N atoms in the porphyrins. The correlation between the strength of electron-withdrawing groups and protonation to N atoms in porphyrins can be described using the spectral patterns of the N 1s XPS and N K XANES spectra.     

Spectrophotometric determination of arsenic in water samples based on micro particle formation of ethyl violet-molybdoarsenate.

In this study, a simple and sensitive method for the determination of arsenic in water samples was developed. The method is based on the formation of micro particles of Ethyl Violet and molybdoarsenate, which gives an apparently homogeneous blue color to the solution. The absorption of the excess dye gradually decreases due to its conversion to a colorless carbinol species under strongly acidic conditions. Consequently, the sufficiently low reagent blank enables the spectrophotometric determination of arsenic with the detection limit of 4 microg l(-1). The coefficient of variation for the spectrophotometry at 50 microg l(-1) was 3.5% (n = 5). Furthermore, it is possible to detect concentrations as low as 10 microg l(-1) of arsenic visually. Our method will be useful as a simple, rapid, and cost-effective field test of arsenic, requiring no complex apparatus or skilled laboratory support.     

Separation of V(V)-4-(2-pyridylazo)resorcinolato complex from a large excess reagent using an ODS cartridge for high-performance liquid chromatography.

A selective off-line preconcentration technique for the V(V) complex with 4-(2-pyridylazo)resorcinol has been developed and successfully applied to the determination of V(V) in an air-borne sample. The target complex was separated from excess reagent using an ODS cartridge and water as the eluent. The complex was then concentrated on another ODS cartridge using tetrabutylammonium bromide and eluted with methanol; the eluate was applied to a one-drop concentration/HPLC. A detection limit as low as (6.05 +/- 0.82)x 10(-11) M (5 ppt) was achieved.     

Novel dating method for speleothems with microscopic fluorescent annual layers.

Terrestrial carbonate deposits with a banded layer structure can be good tools for the extraction of past environmental information on global and local scales using trace element concentrations and stable isotope ratios. The absolute age dating is most important for the reconstruction of an environmental chronicle. The measurements of fluorescent annual bandings in stalagmites using a microscopic spectrofluorometer with an XY-stage can be a convenient dating method and are especially effective for young samples whose absolute age is very difficult to be determined by other methods. The number of annual bandings was objectively counted using a personal computer. The optimal conditions for the measurements are discussed. The annual banding in stalagmites is caused by the seasonal differences in the fulvic acid concentrations in the dripping water which forms speleothems.     

The synthesis of 2-ethoxy-6,11-dimethyl-7,9-bisdehydroaza[14]annulene and its benzannelated derivatives

Title azaannulenes were synthesized starting from annulenones, and the ¹H-NMR spectra are discussed in connection with tropicity of these annulenes.     

A new tomato pregnane glycoside from the overripe fruits

A new pregnane glycoside has been isolated from the overripe fruits of Cherry tomato (Mini tomato), Lycopersicon esculentum var. cerasiforme (DUNAL) ALEF. The structure was determined to be 3-O-beta-lycotetraosyl 3beta-hydroxy-5alpha-pregn-16-en-20-one on the basis of spectroscopic analysis. The seasonal variation of the tomato saponin is discussed.     

Asymptotic analysis for an extended discrete Lotka–Volterra system related to matrix eigenvalues

The integrable discrete hungry Lotka–Volterra (dhLV) system is easily transformed to the qd-type dhLV system, which resembles the recursion formula of the qd algorithm for computing matrix eigenvalues. Some of the qd-type dhLV variables play a role for assisting the time evolution of the others. This property does not appear in the original dhLV system. In this article, we first show the existence of a centre manifold for the qd-type dhLV system. With the help of the centre manifold theory, we next investigate the local convergence of the qd-type dhLV system, and then clarify the monotonicity related to the qd-type dhLV variables at the final phase of the convergence.