Copper-catalyzed site-selective direct arylation of triptycene

A site-selective direct CH arylation protocol for the triptycene skeleton is developed using copper catalyst and diaryliodonium reagents. With the aid of directing groups, C₃-symmetric trisubstituted triptycenes are selectively synthesized, and the structure was determined by X-ray diffraction analysis. Further derivatization of the installed bromo functionalities is also described

Electrophilic substitution of asymmetrically distorted benzenes within triptycene derivatives

Herein we disclose a unique directing effect of 9-substituted triptycenes in electrophilic substitution to achieve the regioselective functionalization of the triptycene core. The Hirshfeld population analysis was adopted to predict the selectivity in electrophilic substitution. TMS and t-Bu groups were found to considerably accelerate the reaction at C2 positions to produce C3-symmetric isomers. Correlation between distortion and charge distribution within benzene rings was systematically examined.Ueno K., Nishii Y., Miura M.. Electrophilic substitution of asymmetrically distorted benzenes within triptycene derivatives. Organic Letters. 23(9), 3552-3556, (2021), 7 May 2021; ©2021 American Chemical Society. https://doi.org/10.1021/acs.orglett.1c00970

Integral presentation of Experimental Results and Bioinformatic Analyses on _Ciona_ _intestinalis_ Proteins

For the aim of facilitating biologists to find new knowledge through the comprehensive proteomic and transcriptomic data of _Ciona intestinalis_, we have been developing an intuitive and integral view of experimental and bioinformatic results for each protein, which, unlike on human proteins, was incomplete for _Ciona_ proteins. In the presentation, we integrated in a view the experimental results of 2D-PAGE analyses done at Shimoda Marine Research Center, University of Tsukuba, 3D-view of expressions (3DPL) done by Hotta _et al_., and cross-references with JGI version 1 and ENSEMBL. A total of 1,673 entries of 2D-PAGE and 57 of 3DPL are currently contained in CIPRO database. The information is summarized in a single page for a protein. Together with BLAST results, comparative genomics, expression profiles, domain search results, localization, phylogeny etc., we provide biologists the highly integrated view amongst the existing databases, which facilitates to understand the protein. For example, the 2D-PAGE and the microarray results of the same protein are sometimes different, which implies the spatial or temporal gaps of the expressions between the mRNA and the protein. Besides, two functionalities are implemented. One is an improved 2D-PAGE viewer, which provides the compact view of spots and experimental information, and another is peptide fragment mass search functionality as improved PerMS algorithm by Hozumi _et al_., by enabling detection of seven kinds of modifications and suspected contaminants

Methoxycarbonyl Group as a Conformational Regulator for The Benzene Ring of Triphenylamines

A series of triphenylamine derivatives bearing a methoxycarbonyl group on the benzene ring was synthesized. The structural and physical properties based on the introduction of the methoxycarbonyl group into benzene ring were investigated by single crystal X-ray diffraction, computational studies and spectroscopic methods. It was revealed that the methoxycarbonyl group has not only structural control but also a definite electronic effect on the triphenylamine structure

Changes in Membrane Potentials and Mechanical Responses of Guinea Pig Atria During Anaphylaxis in Vitro

The anaphylactic reaction in the isolated atria of sensitized guinea pigs is principally to cause acceleration of cardiac activities as already reported. The present attempt was made to observe changes in transmembrane action potentials (AP) and mechanical responses of the atria during the anaphylaxis. Four types of changes in AP were found in spontaneously beating atria that is prolongation of AP at all points of the repolarization, prolongation of the duration with proceeding of repolarization, shortening of the duration at first half, and no change at all in AP pattern. However the change in electrically driven left atria was only a parallel prolongation of the duration to the control in repolarization phase. On the other hand, an increase in the rate shortend the duration of AP in the normal preparation electrically driven. The essential change of the contour of AP in the anaphylactic reaction is the prolongation of AP in repolarization phase. Histamine induced a similar reaction in electrical and mechanical responses to the anaphylactic reaction

Incorporating Community Annotation Interfaces into the CIPRO2.5 Database with Comprehensible Sketches to Support Quick Annotations of Proteome Data.

User annotation or comment interfaces are now widely used in several web sites such as journals, news, weblogs and Wikipedia. However, there are only a few biological databases with annotation interfaces. The _Ciona_ _intestinalis_ protein database (CIPRO) was created in order to provide integrated proteome data especially for experimental biologists. The current database contains 89,673 unique sequences covering all the known and predicted gene models. Typical tasks include which gene models are reliable and which function is plausible. The human-curated annotation is most important for the meaningful database.
Here we incorporate three new functions into the CIPRO2.5 database (http://cipro.ibio.jp/2.5/), providing enriched resources for the users. First, a community annotation interface as web forms and a user comment editor with rating its comment were added. Second, the web pages were specifically designed to compact for quickly understood overviews. For example, cytolocalization was automatically provided by a color-depicted cell image based on the intensity instead of the numeric values of raw data. The expression data of EST, microarray and 2D-PAGE were integrated as one chart. In addition to these data, the images of transmembrane prediction, domain and motif search, and the OMIM ortholog on the chromosome map were included in each protein page. The last, even the BLAST and PMF search were added to combined fields in the retrieval system.
As a result, a total of 11,134 pages were annotated by our community. Furthermore, 2,186 comments were added to the database. Those annotated data are freely accessible at the CIPRO2.5 web site

Spicule Dynamics over Plage Region

We studied spicular jets over a plage area and derived their dynamic characteristics using Hinode Solar Optical Telescope (SOT) high-resolution images. The target plage region was near the west limb of the solar disk. This location permitted us to study the dynamics of spicular jets without the overlapping effect of spicular structures along the line of sight. In this work, to increase the ease with which we can identify spicules on the disk, we applied the image processing method `MadMax' developed by Koutchmy et al. (1989). It enhances fine, slender structures (like jets), over a diffuse background. We identified 169 spicules over the target plage. This sample permits us to derive statistically reliable results regarding spicular dynamics. The properties of plage spicules can be summarized as follows: (1) In a plage area, we clearly identified spicular jet features. (2) They were shorter in length than the quiet region limb spicules, and followed ballistic motion under constant deceleration. (3) The majority (80%) of the plage spicules showed the cycle of rise and retreat, while 10% of them faded out without a complete retreat phase. (4) The deceleration of the spicule was proportional to the velocity of ejection (i.e. the initial velocity).Comment: 12 pages, 9 figures, accepted for publication in PAS

Phenotypes of pain behavior in phospholipase C-related but catalytically inactive protein type 1 knockout mice

Phospholipase C-related inactive protein (PRIP) plays important roles in trafficking to the plasma membrane of GABAA receptor, which is involved in the dominant inhibitory neurotransmission in the spinal cord and plays an important role in nociceptive transmission. However, the role of PRIP in pain sensation remains unknown. In this study, we investigated the phenotypes of pain behaviors in PRIP type 1 knockout (PRIP-1 -/- ) mice. The mutant mice showed hyperalgesic responses in the second phase of the formalin test and the von Frey test as compared with those in wild-type mice. In situ hybridization studies of GABAA receptors revealed significantly decreased expression of γ2 subunit mRNA in the dorsal and ventral horns of the spinal cord in PRIP-1 -/- mice, but no difference in α1 subunit mRNA expression. β2 subunit mRNA expression was significantly higher in PRIP-1 -/- mice than in wild-type mice in all areas of the spinal cord. On the other hand, the slow decay time constant for the spontaneous inhibitory current was significantly increased by treatment with diazepam in wild-type mice, but not in PRIP-1 -/- mice. These results suggest that PRIP-1 -/- mice exhibit the changes of the function and subunits expression of GABAA receptor in the spinal cord, which may be responsible for abnormal pain sensation in these mice

Copper-Catalyzed Asymmetric Sulfonylative Desymmetrization of Glycerol

Glycerol is the main side product in the biodiesel manufacturing process, and the development of glycerol valorization methods would indirectly contribute the sustainable biodiesel production and decarbonization. Transformation of glycerol to optically active C3 units would be one of the attractive routes for glycerol valorization. We herein present the asymmetric sulfonylative desymmetrization of glycerol by using a CuCN/(R,R)-PhBOX catalyst system to provide an optically active monosulfonylated glycerol in high efficiency. A high degree of enantioselectivity was achieved with a commercially available chiral ligand and an inexpensive carbonate base. The optically active monosulfonylated glycerol was successfully transformed into a C3 unit attached with differentially protected three hydroxy moieties. In addition, the synthetic utility of the present reaction was also demonstrated by the transformation of the monosulfonylated glycerol into an optically active synthetic ceramide, sphingolipid E