Flying-seed-like liquid crystals. Part 4:dagger a novel series of bulky substituents inducing mesomorphism instead of using long alkyl chains

We synthesized a novel series of flying-seed-like derivatives (3a-g) based on phthalocyaninato copper(II) (abbreviated as PcCu) substituted by bulky groups {PhO (a), (o-C-1)PhO (b), (m-C-1)PhO (c), (p-C-1)PhO (d), [m, p-(C-1)(2)]PhO (e), [m, m'-(C-1)(2)]PhO (f), and [m,p,m'-(C-1)(3)]PhO (g)} instead of using long alkyl chains, in order to investigate their mesomorphism. Their phase transition behaviour and the mesophase structures were established using a polarizing optical microscope, a differential scanning calorimeter, a thermogravimetry analyser and a temperature-dependent small angle X-ray diffractometer. It was demonstrated that (PhO)(8)PcCu (3a) and [(p-C-1)PhO](8)PcCu (3d) show no mesophase, whereas [(m-C-1)PhO](8)PcCu (3c), {[m,p-(C-1)(2)]PhO}(8)PcCu (3e), {[m,m'-(C-1)(2)]PhO}(8)PcCu (3f), and {[m, p, m'-(C-1)(3)] PhO}(8)PcCu (3g) show various kinds of columnar mesophases of Col(ro)(P2(1)/a), Col(ro)(P2(1)/a), Col(ro)(C2/m) and Col(tet.o), respectively, while [(o-C-1)PhO](8)PcCu (3b) shows a monotropic Col(ro)(P2m) mesophase. Thus, we revealed that mesomorphism could be induced by these novel bulky substituents instead of using long alkyl chains, and that the mesophase structures were greatly affected by the number and position of the methoxy groups. In particular, it is very interesting that the derivatives with methoxy group(s) at the meta position(s), namely, 3c, 3e, 3f and 3g, tend to show enantiotropic mesophase(s), whereas neither the derivative with no methoxy group, 3a, nor the derivative with a methoxy group at the para position, 3d, show a mesophase.ArticleRSC ADVANCES. 5(18):13828-13839 (2015)journal articl

Flying-seed-like liquid crystals 3: new guideline for the induction of mesomorphism by using bulky groups instead of long alkyl chains

In our previous work, we synthesized a series of phthalocyanine-based flying-seed-like compounds, (nPh-PhO)(4)PcCu (n = 3, 2, 1 and 0 in nPh-PhO: a-d), and revealed that each of them shows a columnar liquid crystalline phase (Col(ho) or Col(rho)) from rt to an extremely high temperature near 500 degrees C. Thus, we could obtain columnar liquid crystalline phases for discotic compounds by using bulky substituents (a-d) instead of long alkyl chains. In order to further study the utility of these bulky substituents (a-d) on the induction of mesomorphism for other shaped molecules, we have synthesized novel flying-seed-like calamitic phenoxybenzoic acid derivatives, nPh-PhOBA (3a-d), and their Mitsubishi-Mark-shaped terbium complexes, (nPh-PhOBA)(3)Tb center dot mMeOH (4a-d), in this work. Very interestingly, the mesomorphism of the phenoxybenzoic aids derivatives nPh-PhOBA (n = 0-3) was induced to show a mesophase (M-x) only by the bulky substituent d (n = 0), whereas the mesomorphism of their corresponding terbium complexes (nPh-PhOBA)(3)Tb(III) (n = 0-3) was induced to show rectangular columnar (Col(r)) mesophases by the bulky substituents c and d (n = 1, 0). On the other hand, the mesomorphism of the PcCu complexes (nPh-PhOBA)(4)PcCu (n = 0-3) in our previous work was induced by all the bulky substituents a, b, c and d (n = 0-3). Thus, it becomes apparent that both calamitic and columnar mesomorphism can be induced by the substitution of bulky groups instead of long alkyl chains, and that the balance of the core size and the bulkiness of the substituents is very important to obtain mesomorphism in flying-seed-like compounds. We believe that this is a new guideline for the induction of mesomorphism by using bulky groups instead of long alkyl chains.ArticleJOURNAL OF MATERIALS CHEMISTRY C. 1(34):5315-5321 (2013)journal articl

Discotic liquid crystals of transition metal complexes 51(dagger): Synthesis and mesomorphism of flat-pumpkin-shaped phthalocyanine-fullerene dyads

We have synthesized a novel type of donor-acceptor liquid crystalline material, phthalocyanine-fullerene (Pc-C-60) dyad, [m,p,m'-(C14O)(3)PhO](6)PcCu-C-60 (7), and the Pc precursors, [m,p,m'-(C14O)(3)PhO](6)PcCu-OFBA (6) and [m,p,m'-(C14O)(3)PhO](6)PcCu-OH (5), and established their mesomorphism by using a polarizing optical microscope, a differential scanning calorimeter and a small angle X-ray diffractometer. Very interestingly, their corresponding previous parent Pc derivative, [m,p,m'-(C14O)(3)PhO](8)PcCu (4), shows a very wide temperature region ca. 90 degrees C of a bicontinuous Cub(Pn3m) mesophase, whereas the present children Pc precursors (5 and 6) and Pc-C-60 dyad 7 show not the Cub mesophase but a Col(ho) mesophase. It is also noteworthy that the staking distance in the Col(ho) mesophase of the Pc-C-60 dyad 7 was a very big value of ca. 9.1 angstrom, which is the biggest in discotic liquid crystals to our best knowledge. It may be originated from the biggest excluded volume caused by thermal fluctuation of peripheral long alkoxy chains at m, m'-positions. The excluded volume caused by thermal fluctuation of the peripheral long chains is so big that the molecular shape of the Pc derivative 4 and the Pc-C-60 dyad 7 very resembles a flat pumpkin.ArticleJOURNAL OF PORPHYRINS AND PHTHALOCYANINES. 18(10-11):856-868 (2014)journal articl

Altered functional organization within the insular cortex in adult males with high-functioning autism spectrum disorder: evidence from connectivity-based parcellation

Determination of the optimal number of clusters based on VI and MI in intracalcarine cortex. The intracalcarine cortex was selected as a control region. The VI and MI values are shown for every clustering solution for k values ranging from 2 to 10. Arrows indicate either local minima of VI or local maxima of MI. Dashed lines denote the optimal number of solutions as determined using both VI and MI. The error bars denote standard errors of the mean for 100 repetitions of the split-half procedure (see the “Estimation of the optimal number of clusters” section). “n.s.” indicates no statistically significant difference between points. (PDF 334 kb

Loss of Parp-1 affects gene expression profile in a genome-wide manner in ES cells and liver cells

BACKGROUND: Many lines of evidence suggest that poly(ADP-ribose) polymerase-1 (Parp-1) is involved in transcriptional regulation of various genes as a coactivator or a corepressor by modulating chromatin structure. However, the impact of Parp-1-deficiency on the regulation of genome-wide gene expression has not been fully studied yet. RESULTS: We employed a microarray analysis covering 12,488 genes and ESTs using mouse Parp-1-deficient (Parp-1(-/-)) embryonic stem (ES) cell lines and the livers of Parp-1(-/- )mice and their wild-type (Parp-1(+/+)) counterparts. Here, we demonstrate that of the 9,907 genes analyzed, in Parp-1(-/- )ES cells, 9.6% showed altered gene expression. Of these, 6.3% and 3.3% of the genes were down- or up-regulated by 2-fold or greater, respectively, compared with Parp-1(+/+ )ES cells (p < 0.05). In the livers of Parp-1(-/- )mice, of the 12,353 genes that were analyzed, 2.0% or 1.3% were down- and up-regulated, respectively (p < 0.05). Notably, the number of down-regulated genes was higher in both ES cells and livers, than that of the up-regulated genes. The genes that showed altered expression in ES cells or in the livers are ascribed to various cellular processes, including metabolism, signal transduction, cell cycle control and transcription. We also observed expression of the genes involved in the pathway of extraembryonic tissue development is augmented in Parp-1(-/- )ES cells, including H19. After withdrawal of leukemia inhibitory factor, expression of H19 as well as other trophoblast marker genes were further up-regulated in Parp-1(-/- )ES cells compared to Parp-1(+/+ )ES cells. CONCLUSION: These results suggest that Parp-1 is required to maintain transcriptional regulation of a wide variety of genes on a genome-wide scale. The gene expression profiles in Parp-1-deficient cells may be useful to delineate the functional role of Parp-1 in epigenetic regulation of the genomes involved in various biological phenomena

A systematic review of nonrandomized controlled trials on the curative effects of aquatic exercise

Hiroharu Kamioka1, Kiichiro Tsutani2, Yoshiteru Mutoh3, Hiroyasu Okuizum4, Miho Ohta5, Shuichi Handa4, Shinpei Okada6, Jun Kitayuguchi7, Masamitsu Kamada7, Nobuyoshi Shiozawa8, Sang-Jun Park4, Takuya Honda4, Shoko Moriyama41Faculty of Regional Environment Science, Tokyo University of Agriculture, Tokyo, Japan; 2Department of Drug Policy and Management, Graduate School of Pharmaceutical Sciences, 3Department of Physical and Health Education, Graduate School of Education, The University of Tokyo, Tokyo, Japan; 4Mimaki Onsen (Spa) Clinic, Tomi City, Japan; 5Laboratory of Aqua, Health, and Sports Medicine, 6Physical Education and Medicine Research Foundation, Nagano, Japan; 7Physical Education and Medicine Research Center Unnan, Unnan City, Japan; 8Department of Longevity and Social Medicine, Okayama University Graduate School of Medicine, Dentistry and Pharmaceutical Sciences, Okayama, JapanBackground: The objectives of this review were to integrate the evidence of curative effects through aquatic exercise and assess the quality of studies based on a review of nonrandomized controlled trials (nRCTs).Methods: Study design was a systematic review of nonrandomized controlled trials. Trials were eligible if they were nonrandomized clinical trials. Studies included one treatment group in which aquatic exercise was applied. We searched the following databases from 2000 up to July 20, 2009: MEDLINE via PubMed, CINAHL, and Ichushi-Web.Results: Twenty-one trials met all inclusion criteria. Languages included were English (N = 9), Japanese (N = 11), and Korean (N = 1). Target diseases were knee and/or hip osteoarthritis, poliomyelitis, chronic kidney disease, discomforts of pregnancy, cardiovascular diseases, and rotator cuff tears. Many studies on nonspecific disease (healthy participants) were included. All studies reported significant effectiveness in at least one or more outcomes. However results of evaluations with the TREND and CLEAR-NPT checklists generally showed a remarkable lack of description in the studies. Furthermore, there was the problem of heterogeneity, and we were therefore not able to perform a meta-analysis.Conclusion: Because there was insufficient evidence on aquatic exercise due to poor methodological and reporting quality and heterogeneity of nRCTs, we were unable to offer any conclusions about the effects of this intervention. However, we were able to identify problems with current nRCTs of aquatic exercise, and propose a strategy of strengthening study quality, stressing the importance of study feasibility as a future research agenda objective.Keywords: aquatic exercise, systematic review, nonrandomized controlled trials&nbsp

Metastatic Renal Cell Carcinoma to the Left Sphenoid Sinus: A Case Report in Light of the Literature

A 79-year-old Japanese woman presented with a rare case of metastatic renal cell carcinoma to the left sphenoid sinus with left nasal bleeding. She had previously had right radical nephrectomy for renal cell carcinoma at the age of 64 years and brain and spinal cord infarction at 74 years. Endoscopic examination revealed no mass in the nasal cavity. CT and MRI revealed a tumor in the left sphenoid sinus. The size of the tumor increased gradually from 12 to 15 years after the radical nephrectomy. Complete resection with endoscopic surgery was performed without preoperative embolization. The tumor cells had clear cytoplasm and were arranged in a trabecular pattern lined by a layer of endothelial cells. These findings were identical to the pathological findings of the surgical specimen of the renal cell carcinoma from 15 years previous. A pathological diagnosis of metastatic renal cell carcinoma of clear cell type (grade 1) was made. PET-CT demonstrated no metastasis. The patient’s condition was successfully managed with excision of the tumor, and she remains well with no evidence of recurrence and metastasis 36 months after treatment. Metastatic renal cell carcinoma to the sphenoid sinus is rare, but it might be considered in the differential diagnosis of masses in the paranasal sinus even long after initial treatment of renal cancer

How Can We Cope with Doping in Sports ?

This research has thoroughly studied the actual situation and the recent trends of doping in sports, looking closely into the responses taken by the parties concerned in recent doping cases and throwing light upon the backgrounds and the very essence of doping itself. The aim of this study is to indicate the task we are facing in the fight against doping. The banned substances and procedures of doping has both increased and diversified in the recent years, and so is the percentage of actual positive test results increasing. Doping in sports has spread across the globe. Japan is not an exception to this; there has been cases where a competitor has tested to be positive. Many of the anti-doping activities are taking place, including doping control, and these activities are being reinforced. However, when looking closely into the responses taken by the parties concerned in major doping cases in the past, such as the case of Canadian sprinter Ben Johnson, we have noticed that not in all cases were the responses taken fairly and impartially acording to the regulations and prescribed procedures. The commercialism, nationalism! and heroism of modern sports and the competitors\u27attitude to "rely on materials" cause temptations towards doping and are the backgrounds of doping. We have reached the conclusion, that it is necessary to fully recognize the immorality of doping in both regions of sports competition and medicine, and the fact that doping is an act of depriving the competitor of his/her liberty, humanity and human rights. And this recognition must be passed on to the competitors and instructors through appropriate education