Visualization of dynamic change in contraction-induced lipid composition in mouse skeletal muscle by matrix-assisted laser desorption/ionization imaging mass spectrometry

Lipids in skeletal muscle play a fundamental role both in normal muscle metabolism and in disease states. Skeletal muscle lipid accumulation is associated with several chronic metabolic disorders, including obesity, insulin resistance, and type 2 diabetes. However, it is poorly understood whether the lipid composition of skeletal muscle changes by contraction, due to the complexity of lipid molecular species. In this study, we used matrix-assisted laser desorption/ionization imaging mass spectrometry (MALDI-IMS) to investigate changes in skeletal muscle lipid composition induced by contraction. We successfully observed the reduction of diacylglycerol and triacylglycerol, which are generally associated with muscle contraction. Interestingly, we found the accumulation of some saturated and mono-unsaturated fatty acids and poly-unsaturated fatty acids containing phosphatidylcholine in contracted muscles. Moreover, the distributions of several types of lipid were changed by contraction. Our results show that changes in the lipid amount, lipid composition, and energy metabolic activity can be evaluated in each local spot of cells and tissues at the same time using MALDI-IMS. In conclusion, MALDI-IMS is a powerful tool for studying lipid changes associated with contractions.     

Four new eremophilane-type alcohols from Cremanthodium helianthus collected in China

Four new eremophilane-type sesquiterpenoid alcohols were isolated from Cremanthodium helianthus collected in China and their structures established on the basis of spectroscopic analyses. All of them had 9-en-8-one partial structures with one more double bond either delta11, delta11(13), or delta7(11). Two of them had a hydroxy group at C-1 position.     

Confocal full‐field X‐ray microscope for novel three‐dimensional X‐ray imaging

A confocal full‐field X‐ray microscope has been developed for use as a novel three‐dimensional X‐ray imaging method. The system consists of an X‐ray illuminating `sheet‐beam' whose beam shape is micrified only in one dimension, and an X‐ray full‐field microscope whose optical axis is normal to the illuminating sheet beam. An arbitral cross‐sectional region of the object is irradiated by the sheet‐beam, and secondary X‐ray emission such as fluorescent X‐rays from this region is imaged simultaneously using the full‐field microscope. This system enables a virtual sliced image of a specimen to be obtained as a two‐dimensional magnified image, and three‐dimensional observation is available only by a linear translation of the object along the optical axis of the full‐field microscope. A feasibility test has been carried out at beamline 37XU of SPring‐8. Observation of the three‐dimensional distribution of metallic inclusions in an artificial diamond was performed.     

Flame-spread limit from interactive burning droplets in microgravity

This research conducted microgravity experiments on the flame spread over droplet-cloud elements with strong droplet interaction aboard Kibo on the ISS. The droplet-cloud element represents a local droplet pattern appearing in randomly distributed droplet clouds near the group-combustion-excitation limit and consists of small-droplet-spacing droplets and large-droplet-spacing droplets. As droplet-cloud elements, we used four n-decane droplets, Droplets C, B, A and L, placed at fiber intersections of two-dimensional SiC-fiber lattice with a 4-mm fiber interval in a combustion chamber. The flame spreads over the droplet-cloud element in order of Droplets C, B, A and L. The position of Droplet L relative to Droplet A was varied to investigate the flame-spread-limit distribution around burning Droplet A. The position of Droplet B relative to Droplet A was varied to investigate the effect of two-droplet interaction between Droplets B and A on the flame spread to Droplet L. The position of Droplet C relative to Droplet B was also varied to investigate the effect of three-droplet interaction among Droplets C, B and A. The results shows that in the case with the strong interaction by two or three interactive droplets, the high-temperature region is enlarged by the droplet interaction, centers near the center of mass of the interactive droplets and plays an important role in the flame-spread-limit distribution. Since the burning lifetime of Droplet A is finite, the flame-spread time from burning Droplet A to Droplet L is limited by burning lifetime of Droplet A and is less than 80% of the burning lifetime of Droplet A, which increases with the interactive effect. The flame-spread-limit distance from the center of mass of the interactive droplets increases with the burning lifetime.     

Crystal and molecular structure of an (S)-(+)-enantiomer of modafinil, a novel wake-promoting agent

The (+)-enantiomer of modafinil [(RS)-2-(diphenylmethylsulfinyl)acetamide], a novel wake-promoting agent, was clarified to be S-configuration by X-ray crystal structure analysis. The crystal consists of two crystallographically independent conformers that are different at the torsion angles around the sulfinylacetamide moiety, and this results from the molecular packing requirement to form a two-dimensional hydrogen-bonding network via neighboring amide groups in the crystal. The crystal structure is characterized by the formation of alternative hydrophobic and hydrophilic layers, which are formed among the symmetry-translated assemblies of diphenylmethyl and sulfinylacetamide moieties, respectively. The spatial orientation between the diphenyl and amide groups is believed to be important for the activity of modafinil.     

Chrysophanol glycosides from callus cultures of monocotyledonous Kniphofia spp. (Asphodelaceae)

We established callus cultures of the monocotyledonous plants Kniphofia foliosa and K. tuckii (Asphodelaceae), which produce the anthraquinone derivatives chrysophanol and its glycosides. The minor product chrysophanol 8-O-beta-gentiobioside was fully characterized by spectroscopic analysis and synthesis.     

Facile deoxygenation of dicarbonyl compounds using a samarium diiodide-additive system

The reduction of alpha- and beta-dicarbonyl compounds was investigated with samarium diiodide in the presence of additive. Diketones and ketocarboxylic acids were easily reduced at room temperature to give the mono-alcohols in good to excellent yield, and ketoester afforded the saturated ester as the major product in moderate yield. These reductions containing the reductive deoxygenation can be rapidly performed under the facile and mild conditions by this method.     

Regression analysis of enzyme reaction. O-methylation of catechol derivatives by catechol-O-methyltransferase

The electronic structures of catechol derivatives, 3,4-dihydroxy-1-substituted benzenes, including epinephrine and norepinephrine, were calculated by means of the CNDO /2 and the MINDO /3 methods. Correlation between the maximum velocities divided by the molecular weight, as between the inverse of Michaelis–Menten constants in the O-methylation reaction catalyzed by catechol-O-methyltransferase and the electronic indices calculated on the basis of the frontier electron theory was found. The correlation coefficient between the observed maximum velocities divided by the molecular weight and the calculated ones was 0.873. The regression analysis showed that the Coulombic forces at the C₃ and C₄ positions and the electron acceptable indices at C₆ and meta-O positions represented the best correlation with the biological activities (V_max and K_m). The electronic indices of the catechol moieties represent the rate-limiting factor of the O-methylation reaction.     

Conformational Features of 7,8,13β,14α-Tetrahydro-N7-methylcorysaminium,a biosynthetic intermediate to the protopine-type alkaloid corycavine

The crystal structure of (±)-7,8,13β,14α-tetrahydro-N⁷-(¹³C)methylcorysaminium iodide (¹³C- 3a ·I) was investigated by X-ray analysis and thus the relative configuration (7S*,13S*,14S*) established (Fig. 1). The conformation of 3a was shown to have a cis-junction of the B/C rings and the rings A and D in an antiperiplanar position relative to the C(13)? C(14) bond (‘anti-cis’), a twisted half-chair for ring B, and a half-chair for ring C (Figs. 2 and 3). Conformation analysis by ¹H-NMR data indicated that the crystal conformation of 3a is also the preferred one in MeOH solution.