Octakis(2,6-diethylphenyl)octastannacubane

Thermolysis of hexakis(2,6diethylphenyl)-cyclotristannane (2) in naphthalene provides red octakis-(2,Gdiethylphenyl)octastannacubane (l), which has been fully characterized, including crystallographic analysis. Compound 1 represents the first example of the organostannane cluster series (RSn)_n

Bis(μ2-4,7-dimethyl-4,7-diazadecane-1,10-dithiolato)trinickel(II) bis(perchlorate)

In the title compound, [Ni3(C10H22N2S2)2](ClO4)2, the complex cation consists of a nickel(II) ion and two [Ni(C10H22N2S2)] units with an N2S2 tetra­dentate ligand, 3,3′-[1,2-ethane­diylbis(methyl­imino)]bis­(1-propane­thiol­ate). The central NiII ion is located on a crystallographic inversion centre and is bound to the four S atoms of the two [Ni(C10H22N2S2)] units to form a linear sulfur-bridged trimetallic moiety. The dihedral angle between the central NiS4 plane and the terminal NiN2S2 plane is 145.71 (5)°. In the [Ni(C10H22N2S2)] unit, the two methyl groups on the chelating N atoms are cis to each other, and the two six-membered N,S-chelate rings adopt a chair conformation. The Ni—S bond lengths and the S—Ni—S bite angles in the central NiS4 group are similar to those in the [Ni(C10H22N2S2)] unit

Octakis(2,6-diethylphenyl)octastannacubane

Thermolysis of hexakis(2,6diethylphenyl)-cyclotristannane (2) in naphthalene provides red octakis-(2,Gdiethylphenyl)octastannacubane (l), which has been fully characterized, including crystallographic analysis. Compound 1 represents the first example of the organostannane cluster series (RSn)_n

(η6-Benzene){2-[2-(tert-butyl­sulfan­yl)phenyl]pyridine-κ2 N,S}chlorido­ruthenium(II) hexa­fluorido­phosphate

In the title compound, [RuCl(C6H6)(C15H17NS)]PF6, the cation adopts a three-legged piano-stool structure around the Ru(II) atom with an η6-benzene ligand, a chloride ligand and a 2-[2-(tert-butyl­sulfan­yl)phen­yl]pyridine (btppy) ligand. The btppy ligand acts as a N,S-bidentate ligand, forming a six-membered ring, which has an envelope conformation. The S—Ru—N bite angle is 86.76 (9)°, and the dihedral angle between the pyridine and benzene rings in btppy is 39.8 (2)°. The unit cell contains two pairs of racemic diastereomers with (S Ru,S S) and (R Ru,R S) configurations, in which the tert-butyl group on the coordin­ated S atom is distant from the η6-benzene ligand

Effects of valproic acid on the cell cycle and apoptosis through acetylation of histone and tubulin in a scirrhous gastric cancer cell line

Background. Management of peritoneal dissemination is the most critical problem in gastric cancer. This study was performed to investigate the inhibitory effects of valproic acid (VPA) on a highly peritoneal-seeding cell line of human scirrhous gastric cancer, OCUM-2MD3, and to explore the mechanism and the potential of VPA. Methods. The effects of VPA on the growth of OCUM-2MD3 cells were assessed by MTT assay. In addition, paclitaxel (PTX) was combined with VPA to evaluate their synergistic effects. HDAC1 and HDAC2 expression were evaluated by western blotting in OCUM-2MD3 cells and other gastric cancer cell lines (TMK-1, MKN-28). The acetylation status of histone H3 and α-tubulin after exposure to VPA were analyzed by western blotting. The activities of cell cycle regulatory proteins and apoptosis-modulating proteins were also examined by western blotting. The effects of VPA in vivo were evaluated in a xenograft model, and apoptotic activity was assessed by TUNEL assay. Results. OCUM-2MD3 cells showed high levels of HDAC1 and HDAC2 expression compared with TMK-1 and MKN-28. The concentration of VPA required for significant inhibition of cell viability (P < 0.05) was 5 mM at 24 h and 0.5 mM at 48 h and 72 h. The inhibition of VPA with PTX showed dose-dependent and combinatorial effects. VPA increased acetyl-histone H3, acetyl α-tubulin, and p21WAF1 levels accompanied by upregulation of p27, caspase 3, and caspase 9, and downregulation of bcl-2, cyclin D1, and survivin. In the xenograft model experiment, the mean tumor volume of the VPA-treated group was significantly reduced by 36.4%, compared with that of the control group at 4 weeks after treatment (P < 0.01). The apoptotic index was significantly higher in the VPA-treated group (42.3% ± 3.5%) than in the control group (7.7% ± 2.5%) (P < 0.001). Conclusions. VPA induced dynamic modulation of histone H3 and α-tubulin acetylation in relation with the anticancer effect and the enhancement of PTX in the OCUM-2MD3 cell line. Therefore, VPA in combination with PTX is expected to be a promising therapy for peritoneal dissemination of scirrhous gastric cancer. © 2010 Yagi et al; licensee BioMed Central Ltd

Disentangling the 1MLCT transition of [Ru(bpy)3]2+ by Stark absorption spectroscopy

金沢大学理工研究域物質化学系The metal-to-ligand charge transfer (MLCT) transition of [Ru(bpy)3]2+ was investigated using Stark absorption spectroscopy, where bpy is the abbreviation of 2,2\u27-bipyridyl ligand. The magnitude and direction of the photoinduced intramolecular charge transfer were precisely determined for the 1MLCT transition of [Ru(bpy)3]2+. The 1MLCT absorption band of [Ru(bpy)3]2+, observed in the 18,000-30,000cm-1 spectral region, is composed of several sub-bands that can be approximated with Gaussian profiles. In particular, three distinct major 1MLCT bands of [Ru(bpy)3]2+ (g4, 21272cm-1; g5, 22026cm-1; g7, 23448cm-1) could be distinguished by the direction of the charge transfer of each transition. The experimentally determined directions of charge transfer showed good agreement with the theoretical prediction by Kober and Meyer. We also re-examined the phosphorescence and the excitation spectra of [Ru(bpy)3]2+. The 1MLCT excited states of the g5 and g7 bands almost completely transform to 3MLCT excited states, and then 40% of the 3MLCT state relaxes to the ground state by emitting phosphorescence. 46% of 1MLCT excited state of the g4 band non-radiatively relaxes to the ground state. These results provide good support for the assignment of the different origins of the g4 and other two Gaussian sub-bands (g5 and g7). © 2017 Elsevier B.V.in Press / Embargo Period 12 month

Efficacy of pre-operative chemotherapy with docetaxel, cisplatin, and S-1 (DCS therapy) and curative resection for gastric cancer with pathologically positive para-aortic lymph nodes

Background: The prognosis of gastric cancer with para-aortic lymph node (PAN) metastasis is poor. We applied triple combination chemotherapy with docetaxel, cisplatin, and S-1 (DCS therapy) as pre-operative chemotherapy and investigated the outcome of the combination of this therapy and gastrectomy with para-aortic lymph node dissection (PAND). Methods: We retrospectively identified 44 patients with pathologically positive PAN who underwent curative surgery at Kanazawa University Hospital between 1990 and 2008. Among the 44 patients, 16 received pre-operative DCS therapy and subsequent surgical resection after two courses of the therapy. Results: Pre-operative DCS therapy showed high clinical response ratio (68.8%) and disease control ratio (100%). The pathological response ratio of resected specimen was 87.5%. At 2 years after surgery, the overall survival ratio was 93.8% and relapse-free survival was 75.0%. Pre-operative DCS therapy was only independent prognostic factor in multivariate analysis. Grade 3/4 toxicity was observed only in 25.0% of patients who underwent DCS therapy. Surgical complication was observed in 31.3% of patients, and this ratio was equal to that of patients who did not receive DCS therapy. Conclusion: Multimodal therapy comprising combined pre-operative DCS therapy and gastrectomy with PAND was extremely effective and feasible for advanced gastric cancer with PAN metastasis. J. Surg. Oncol © 2011 Wiley Periodicals, Inc

Predictive factors for postoperative tachyarrhythmia after thoracoscopic esophagectomy and the usefulness of landiolol hydrochloride for its treatment

Background: Tachyarrhythmia after esophagectomy is a severe complication that should not be underestimated because of its negative impact. The aims of this study were to clarify the cause and impact of postoperative tachyarrhythmia after thoracoscopic esophagectomy. Additionally, we analyzed the usefulness of landiolol administration for postoperative tachyarrhythmia. Methods: We evaluated the predictive factors for tachyarrhythmia onset after surgery and its clinical impact in 127 patients who underwent thoracoscopic esophagectomy with extended lymphadenectomy. Moreover, we analyzed the efficacy of landiolol for postoperative tachyarrhythmia. Results: Tachyarrhythmia developed in 38 of the 127 patients. Multivariate analysis showed that advanced age, heart disease, and hyperlipidemia were associated with postoperative tachyarrhythmia. Hyponatremia, hypoalbuminemia, and leukocytosis on postoperative day 3 were significantly associated with tachyarrhythmia onset. The incidence of all complications and respiratory complications, including pneumonia, was significantly higher in patients with than in those without tachyarrhythmia. The mortality rate in the tachyarrhythmia group tended to be higher than that in the nontachyarrhythmia group. Landiolol as a treatment for tachyarrhythmia immediately decreased heart rate and safely reduced subsequent respiratory complications. Conclusion: In elderly patients with cardiac disease or hyperlipidemia, surgeons should be alert for the occurrence of tachyarrhythmia after esophagectomy. Postoperative tachyarrhythmia is a marker of morbidities with particular emphasis on respiratory complications. However, it can be adequately managed by landiolol, resulting in fewer respiratory complications. Landiolol might be a safe and convenient agent for managing postoperative tachyarrhythmia after thoracoscopic esophagectomy, resulting in lower mortality and morbidity rates. © 2013 The Japan Esophageal Society and Springer