Formation of 1,2,4-trioxolanes via 9,10-dicyanoanthracene(DCA)-sensitized photo-oxygenation of 2,2-diaryl-3-(2,2-diarylvinyl)oxiranes

9,10-Dicyanoanthracene-sensitized photo-oxygenation of 2,2-diaryl-3-(2,2-diarylvinyl)oxiranes 3 in acetonitrile did not afford the corresponding 1,2,4-trioxepines 4, but 1,2,4-trioxolanes 7. The structural assignment of 7 was reported, and the mechanism of the formation of 7 was proposed.     

Evaluation of the Intracellular Signaling Activities of κ-Opioid Receptor Agonists,Nalfurafine Analogs; Focusing on the Selectivity of G-Protein- and β-Arrestin-Mediated Pathways

Opioid receptors (ORs) are classified into three types (μ, δ, and κ), and opioid analgesics are mainly mediated by μOR activation; however, their use is sometimes restricted by unfavorable effects. The selective κOR agonist nalfurafine was initially developed as an analgesic, but its indication was changed because of the narrow safety margin. The activation of ORs mainly induces two intracellular signaling pathways: a G-protein-mediated pathway and a β-arrestin-mediated pathway. Recently, the expectations for κOR analgesics that selectively activate these pathways have increased; however, the structural properties required for the selectivity of nalfurafine are still unknown. Therefore, we evaluated the partial structures of nalfurafine that are necessary for the selectivity of these two pathways. We assayed the properties of nalfurafine and six nalfurafine analogs (SYKs) using cells stably expressing κORs. The SYKs activated κORs in a concentration-dependent manner with higher EC₅₀ values than nalfurafine. Upon bias factor assessment, only SYK-309 (possessing the 3S-hydroxy group) showed higher selectivity of G-protein-mediated signaling activities than nalfurafine, suggesting the direction of the 3S-hydroxy group may affect the β-arrestin-mediated pathway. In conclusion, nalfurafine analogs having a 3S-hydroxy group, such as SYK-309, could be considered G-protein-biased κOR agonists.     

Box-Ball Systems and Robinson-Schensted-Knuth Correspondence

We study a box-ball system from the viewpoint of combinatorics of words and tableaux. Each state of the box-ball system can be transformed into a pair of tableaux (P, Q) by the Robinson-Schensted-Knuth correspondence. In the language of tableaux, the P-symbol gives rise to a conserved quantity of the box-ball system, and the Q-symbol evolves independently of the P-symbol. The time evolution of the Q-symbol is described explicitly in terms of the box-labels.     

Derivatives of Dedekind sums and their reciprocity law

In this paper derivatives of Dedekind sums are defined, and their reciprocity laws are proved. They are obtained from values at non-positive integers of the first derivatives of Barnes’ double zeta functions. As special cases, they give finite product expressions of the Stirling modular form and the double gamma function at positive rational numbers.     

An estimation of the distribution functions of doped Tb and Nd in glasses by fluorescence measurements

The distribution functions of doped Tb³⁺ and Nd³⁺ in silicate, germanate, borate and phosphate glasses, in which cross-relaxation among active ions plays an important role, have been estimated by fluorescence measurements. In order to analyze both the steady state and the transient fluorescence characteristics, a non-linear model for the resonant energy transfer has recently been developed. The experimental fluorescence intensity and decay curves, measured as a function of acceptor concentration, suggested a modified distribution function, which included the effect of the segregation of donors and acceptors. The number of segregated Tb³⁺ ions at the second nearest neighbor position around a Tb³⁺ ion was estimated to be 0.1–3.4, depending on the host glass.     

Mixture Design PARAFAC HPLC-DAD Metabolomic Fingerprints of Fractionated Organic and Basic Extracts from <Emphasis Type="Italic">Erythrina speciosa</Emphasis> Andrews Leaves

HPLC-DAD analysis of statistical mixture design extracts of Erythrina speciosa Andrews leaves provided chromatographic and UV–visible profiles of their basic and organic fractions that were treated with the PARAFAC multivariate method. The design extracts provided greater varieties and amounts of metabolites than could be obtained by classical extraction methods. Fractionation provided more diverse fingerprint information than obtained previously from only the crude extract. The two largest chromatographic peaks, one with a 4.8 min elution time having an intense spectral band at 235 nm and the other a 5.8 min peak with an intense 238 nm band for the basic fraction were obtained with the ternary 1:1:1 ethanol–dichloromethane–hexane mixture. These can be assigned to diene-type and lactonic alkaloids. Peaks with the same retention times are also found in the organic fraction but are extracted with different mixtures and have distinct spectral behavior in the 235 nm region, probably being aromatic alkaloids. The above strategy permits a more unambiguous assignment of metabolic groups to specific chromatographic peaks. This can be expected to provide higher quality chromatographic fingerprints for natural products’ chemistry.     

Analysis of Adsorbed Urea and Alkylthiourea on Alumina Surface by Inelastic Electron Tunneling Spectroscopy

Inelastic electron tunneling spectroscopy is used in the analysis of chemisorbed species of urea and alkylthiourea on the alumina surface using an Al-Al₂O₃-Pb tunnel junction. Tunneling spectra of urea, thiourea, N,N′-dimethylthiourea (DMTU), and tetramethylthiourea (TMTU) were taken and analyzed for designated band positions and intensities by comparing with the corresponding IR spectrum. These molecules seem to exhibit similar adsorption behavior onto alumina surface. Thiourea and urea interact with the surface through the nitrogen lone pairs and orient perpendicularly on the Lewis acid site of the alumina surface. DMTU and TMTU are still adsorbed through the nitrogen atoms, but the molecular plane has a somewhat inclined orientation to the alumina surface.