Electrochemical oxidation of cholesterol in acetonitrile leads to the formation of cholesta-4,6-dien-3-one

Cholesterol was shown to be oxidized at the glassy carbon electrode in an acetonitrile–2-propanol mixture and this oxidation reaction was applied to the determination of serum total cholesterol by high-performance liquid chromatography with electrochemical detection (K. Hojo, H. Hakamata, A. Ito, A. Kotani, C. Furukawa, Y.Y. Hosokawa, F. Kusu, J. Chromatogr. A 1166 (2007) 135–141). To gain insight into the detection mechanisms of cholesterol, an electrolytic product of cholesterol was collected and characterized by infrared spectroscopy, one- and two-dimensional nuclear magnetic resonance, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The three techniques, together with comparisons of literature spectral data, confirmed the formation of cholesta-4,6-dien-3-one. The conversion of cholesterol to cholesta-4,6-dien-3-one, a four-electron, four-proton electrochemical process, has been proposed as an electrochemical oxidation mechanism of cholesterol in acetonitrile.     

The new and improved NIST Dragon's LAIR (Lofting and Ignition Research) facility

Several studies suggest that the firebrands are a major cause of structural ignition of Wildland–Urban Interface fires in USA and Australia. For 40 years, past firebrand studies have focused on how far firebrands fly and do not assess the vulnerabilities of structures to ignition from firebrand showers. The development of the National Institute of Standards and Technology (NIST) Dragon has allowed the quantification of structure ignition vulnerabilities of full‐scale building assemblies. Full‐scale tests are necessary to highlight vulnerabilities of structures to ignition under firebrand attack, whereas bench‐scale test methods afford the capability to test new firebrand‐resistant technologies and may serve as the basis for new standard testing methodologies. To this end, the present investigation was undertaken to construct a new and improved Dragon's Lofting and Ignition Research facility. This entailed removing the NIST Baby Dragon from the wind tunnel facility and inserting the new and improved NIST continuous feed Baby Dragon. The unique feature of the continuous feed Baby Dragon, over the current NIST Baby Dragon, is the capability to produce a constant firebrand shower in order to expose building materials to continual firebrand bombardment. The efficacy of the new experimental facility to determine ignition regime maps of building materials exposed to wind‐driven firebrand showers is presented. Specifically, ignition regime maps are presented as a function of continuous firebrand generation rate, wind tunnel speed, and cedar moisture content. Copyright © 2011 John Wiley & Sons, Ltd.     

Fatty Acid Composition of Plasma,Erythrocytes and Adipose: Their Correlations and Effects of Age and Sex

The composition of fatty acids in abdominal subcutaneous adipose tissue and the correlation of fatty acid values of plasma and erythrocytes had not been reported in Japan. The aim of the present study was to investigate the fatty acid composition and correlation of plasma and erythrocyte phospholipids (PL) and adipose triacylglycerols (TG) in 75 adult patients admitted for non-malignant diseases. We also examined the relationship of n-3 and n-6 polyunsaturated fatty acid (PUFA) with patients’ characteristics. The total n-3 PUFA were 11.2, 11.8 and 1.9%, and the ratios of n-6/n-3 were 2.41, 1.87 and 8.20 in plasma and erythrocyte PL and adipose TG, respectively. There were the highest correlations for total n-3 PUFA and the n-6/n-3 ratio between plasma and erythrocyte PL and adipose TG. There was a positive correlation between n-3 PUFAs and age, but a negative correlation was found between n-6 PUFAs and age. There was no significant difference in the values of PUFAs in plasma and erythrocyte PL and adipose TG between men and women. The patients with cholesterol cholecystolithiasis showed a significantly lower proportion of eicosapentaenoic acid in plasma and erythrocyte PL than those of the other patients. Our findings suggest that PUFA in plasma and erythrocyte PL may be good biomarkers and more acceptable for studying participants than adipose TG.     

Analgesic Mechanisms of Steroid Ointment against Oral Ulcerative Mucositis in a Rat Model

Despite the long history of use of steroid ointments for oral mucositis, the analgesic mechanism has not been fully elucidated. In this study, we examined the effects of triamcinolone acetonide (Tmc) on oral ulcerative mucositis-induced pain in conscious rats by our proprietary assay system. Based on evaluations of the physical properties and retention periods in the oral mucosa of human volunteers and rats, we selected TRAFUL^® ointment as a long-lasting base. In oral ulcerative mucositis model rats, TRAFUL^® with Tmc suppressed cyclooxygenase-dependent inflammatory responses with upregulations of glucocorticoid receptor-induced anti-inflammatory genes and inhibited spontaneous nociceptive behavior. When an ointment with a shorter residual period was used, the effects of Tmc were not elicited or were induced to a lesser extent. Importantly, TRAFUL^® with Tmc also improved oral ulcerative mucositis-induced mechanical allodynia, which has been reported to be independent of cyclooxygenase. Ca²⁺ imaging in dissociated trigeminal ganglion neurons showed that long-term preincubation with Tmc inhibited the hypertonic stimulation-induced Ca²⁺ response. These results suggest that the representative steroid Tmc suppresses oral ulcerative mucositis-induced pain by general anti-inflammatory actions and inhibits mechanical sensitivity in peripheral nerves. For drug delivery, long-lasting ointments such as TRAFUL^® are needed to sufficiently induce the therapeutic effects.     

Facile method for the preparation of 7-methyl-8-oxoguanosines as an immunomodulator

Reaction of 9-(2,3,5-tri-O-acetyl-beta-D-ribofuranosyl)-7-methylguaninium iodide (2a) with hydrogen peroxide in acetic acid gave the corresponding 7-methyl-8-oxoguanosine derivative (3a) in good yield. Deprotection of 3a easily gave 7-methyl-8-oxoguanosine (1), which is well-known as an immunomodulator. Substitution of acetyl group at the N2-position of guanine ring accelerated the oxidation reaction of the 7-methylguaninium iodide.     

Medical image diagnosis of kidney regions by deep feedback GMDH-type neural network using principal component-regression analysis

The deep feedback Group Method of Data Handling (GMDH)-type neural network is applied to the medical image recognition of kidney regions. In this algorithm, the principal component-regression analysis is used for the learning calculation of the neural network, and the accurate and stable predicted values are obtained. The neural network architecture is automatically organized so as to fit the complexity of the medical images using the prediction error criterion defined as Akaike’s Information Criterion (AIC) or Prediction Sum of Squares (PSS). The recognition results show that the deep feedback GMDH-type neural network algorithm is useful for the medical image recognition of kidney regions, because the optimum neural network architecture is automatically organized.     

Bioactivities of nostocine a produced by a freshwater cyanobacterium Nostoc spongiaeforme TISTR 8169

A freshwater cyanobacterium, Nostoc spongiaeforme TISTR 8169, synthesizes and releases a violet pigment, nostocine A, into medium. We examined the bioactivity of nostocine A to several model organisms breeding with N. spongiaeforme in the natural environment. To microalgae, nostocine A exhibited growth inhibitory activity comparable to paraquat, and the activity tended to be stronger to green algae than to cyanobacteria. Nostocine A also exhibited strong inhibitory activity to the root elongation of barnyard grass, strong antifeedant activity to cotton ballworm, and acute toxicity to mice resulting in its classification as a dangerous poison. The results suggest that nostocine A may act as a toxin or an allelochemical to breeding organisms in nature. In a laboratory culture of N. spongiaeforme, the production of nostocine A was enhanced at higher temperature, 30 degrees C, and more intense light, 30 W/m2, than the basal conditions, 25 degrees C and 10 W/m2. Cultivation of cells with H2O2 at 1 or 2 mM also enhanced the production of nostocine A, indicating that nostocine A may be synthesized and released when the cells are exposed to oxidative stress, possibly occurring at higher temperature and more intense light. LC-MS and electron spin resonance analyses revealed that nostocine A, reduced previously by NaBH4, immediately recovered to its original form upon exposure to air and the generation of superoxide radical anions occurred at this re-oxidation step. These results suggest that the adverse effects of nostocine A on various organisms may be related to the function of nostocine A in generating toxic reactive oxygen species, which occurs in the cells of target organisms.