Search

Cyclosiloxanes directly bearing polyaromatic groups on silicon atoms have scarcely been reported. Herein, hexa(1-pyrenyl)cyclotrisiloxane (

A new Rh(III) separation method using metal-containing hydrochloric acid (HCl) solutions has been developed. This method includes Rh(III) precipitation with high selectivity using aromatic primary diamines as precipitants. The compound p-phenylene diamine dihydrochloride (PPDA) successfully precipitates only Rh(III) from HCl solutions containing Pd(II), Pt(IV), and Rh(III). Furthermore, highly selective Rh(III) recovery from the simulated spent catalyst leach solution, comprising Pd, Pt, Rh, Ce, Al, Ba, Zr, La, and Y in 5 M HCl, was achieved using PPDA. Single-crystal X-ray analysis revealed that the Rh(III)-containing precipitate using PPDA forms three-dimensional ionic crystals comprising the [RhCl6]3–/ammonium form of PPDA/chloride anion/H2O at a 1:2:1:2 ratio. Formation of these unique ionic crystals plays a key role in the highly selective Rh(III) recovery. This Rh(III) recovery method will be promising for use in the purification process of Rh as well as the practical Rh recovery from spent catalysts.

Rhodium (Rh) is the most expensive platinum group metal (PGM) and is of great industrial importance. Although the recycling of PGMs from secondary sources is in high demand, the preferential and selective separation of Rh from PGM mixtures remains a great challenge. Here, a selective Rh separation method involving the precipitation of Rh from an HCl solution containing palladium (Pd), platinum (Pt), and Rh is reported. 4-Butylaniline and 4-hexylaniline were used as precipitants for Rh, and selective Rh precipitation was achieved at high HCl concentrations. We revealed that Rh in HCl selectively forms a unique and highly stable ion-pair complex comprising [RhCl6]3-/anilinium/chloride ions in a 1:6:3 ratio. The formation and high stability of the Rh complex were found to play important roles in the selective recovery of Rh from PGM mixtures.

Alkanes composed of C-C and C-H show a low electric polarization, and therefore, there is only very weak interaction between alkanes and adsorbents. Thus, it is difficult to separate a specific alkane from a mixture of alkanes by adsorption. Here, two activated "channel-like" crystals generated from brominated thiacalix[4]arene propyl ethers, which adopt 1,3-alternate and partial cone conformations, recognize specific alkane vapors depending on alkane-shape and -size, sorting in three-type alkane guests such as linear, branched, and cyclic alkanes. Two activated crystals, which are prepared by removal of solvent upon heating under reduced pressure, incorporate branched and/or cyclic alkane vapors by a unique "gate-opening" mechanism via a crystal transformation in the process. Linear alkane vapors do not trigger gate opening and are not taken up by the activated crystals. The shape and size molecular-recognition properties of the activated crystals promises considerable usefulness for the separation of linear, branched, and cyclic alkanes.

Donor-type and acceptor-type 9,9′-bifluorenylidene derivatives, MOBF and CNBF, were synthesized. Suitable energy levels on the excited states of the compounds for singlet fission were revealed by density functional theory calculation. Thermal and optoelectronic properties of the compounds were investigated, and the OPV devices with the donor-type MOBF and the acceptor-type CNBF were fabricated. MOBF showed large dependence of photocurrent on magnetic field, suggesting the singlet fission behavior in the OPV device. On the other hand, CNBF did not show any magnetic field dependence of photocurrent, probably because of poor morphology.

The prognosis of patients with recurrent/persistent endometrial cancer, particularly type II cancer, remains poor, and effective treatment has not yet been established. We herein present the case of a patient with recurrent type II endometrial cancer who received bevacizumab + chemotherapy continued beyond progression, after previously receiving bevacizumab + chemotherapy. This patient experienced recurrence after first- and second-line adjuvant chemotherapy followed by modified radical hysterectomy and she was administered bevacizumab + paclitaxel + carboplatin therapy. After six cycles of treatment, all metastatic lesions shrunk, indicating partial response. The patient next received single-agent bevacizumab as maintenance therapy. After 12 cycles of bevacizumab monotherapy, disease progression was detected; therefore, combination therapy consisting of bevacizumab, doxorubicin and carboplatin was initiated. After six cycles of this combination therapy, the patient exhibited disease stabilization. Finally, 18 months after the initial bevacizumab treatment, the patient remained on combination chemotherapy, without complaints or signs of tumor progression (last follow-up, October 2014).

A cyclic bisurea derivative 2a has been successfully prepared from the corresponding diamine and diisocyanate in the presence of tetrabutylammonium chloride as a template. A more soluble cyclic bisurea 2b has also been prepared by introduction of sterically bulky tert-butyl groups. X-ray crystal analyses of [2a·Cl]− and [2b·Cl]− revealed that overall structure was saddle like and the chloride anion was located in the center of the cavity. The bound chloride anion was hydrogen bonded by four N–H of urea groups and weakly hydrogen bonded by four 1-C–H of naphthyl groups, respectively. After removal of the bound chloride anions of [2b·Cl]− with silver nitrate, two different X-ray crystals of free 2b were obtained; one was intermolecular hydrogen bonded shrunken structure and the other was extended structure. Receptor 2b showed large binding ability for Cl–, however, the selectivity for Cl– against basic anions, such as AcO– and F–, has been insufficient. In aqueous MeCN, the association constant of 2b for Cl...

Low-grade endometrial stromal sarcoma (LGESS) is a rare malignancy. The tumor is reportedly responsive to hormonal therapy, most commonly with medroxyprogesterone acetate (MPA), but the effectiveness of aromatase inhibitors for recurrent LGESS remains unclear. The present study reports a case of stage IC LGESS presenting with abnormal uterine bleeding, and also provides a review of the literature. Following a total abdominal hysterectomy and bilateral salpingo-oophorectomy, MPA therapy was initiated; treatment was successful, but discontinued 19 months later due to disruptive side effects. A further 2 months later, the patient presented with recurrent disease and received chemotherapy. MPA treatment was restarted with a partial response. A second recurrence, 4 years later, presented with lung and para-aortic lymph node metastases. The patient responded to treatment with the aromatase inhibitor letrozole. The patient has since exhibited stable disease and remained free of symptoms for 7 years. This case suggests that aromatase-inhibitor treatment may be effective for recurrent LGESS as a second-line treatment.

The association between neoplastic disease and thromboembolic disorders was first recognized by Trousseau in 1865. Blood coagulation abnormalities have been reported in the majority of patients with cancer, including those with ovarian carcinoma. However, Trousseau's syndrome (TS) has rarely been reported in women with ovarian carcinoma. We herein report a case series of TS, notably in the brain, in association with gynecological malignant disease, and emphasize the difficulties associated with the management of these thromboembolic effects. The aim of this study was to present our experience with 5 TS patients whose condition was effectively controlled through treatment of the primary malignant disease. Therefore, we suggest that patients with TS may be cured by tumor resection, even if they have severe thromboembolic disease, such as cerebral or pulmonary infarction.

The clinicopathological significance of amplification was investigated of the gene encoding cyclin E (CCNE1) and we assessed whether CCNE1 was a potential target in endometrioid endometrial carcinomas. CCNE1 amplification and CCNE1 or F-box and WD repeat domain-containing 7 (FBXW7) expression in endometrial endometrioid carcinoma was assessed by immunohistochemistry and fluorescence in situ hybridization. CCNE1 knockdown by small interfering RNA (siRNA) was used to assess the CCNE1 function. The results showed that CCNE1 amplification was present in 9 (8.3%) of 108 endometrial carcinomas. CCNE1 amplification was correlated with high histological grade (Grade 3; p=0.0087) and lymphovascular space invasion (p=0.0258). No significant association was observed between CCNE1 amplification and FIGO stage (p=0.851), lymph node metastasis (p=0.078), body mass index (p=0.265), deep myometrial invasion (p=0.256), menopausal status (p=0.289) or patient age (p=0.0817). CCNE1 amplification was significantly correlated with shorter progression-free and overall survival (p=0.0081 and 0.0073, respectively). CCNE1 protein expression or loss of FBXW7 expression in endometrial endometrioid carcinoma tended to be correlated with shorter progression-free and overall survival; however, this difference was not statistically significant. Multivariate analysis showed that CCNE1 amplification was an independent prognostic factor for overall survival but not for progression-free survival (P=0.0454 and 0.2175, respectively). Profound growth inhibition was observed in siRNA-transfected cancer cells with endogenous CCNE1 overexpression compared with that in cancer cells having low CCNE1 expression. CCNE1 amplification was independent of p53, HER2, MLH1 and ARID1A expression but dependent on PTEN expression in endometrial carcinomas. These findings indicated that CCNE1 amplification was critical for the survival of endometrial endometrioid carcinomas. Furthermore, the effects of CCNE1 knockdown were dependent on the CCNE1 expression status, suggesting that CCNE1-targeted therapy may be beneficial for patients with endometrial endometrioid carcinoma having CCNE1 amplification.

The inclusion behavior of pyridine N-oxide in the cavity of hetero-alkalimetallic (Na, K) sulfonatothiacalix[4]arene was studied by single crystal X-ray diffraction. This hetero-alkali metallic host–guest assembly (3) was mainly supported by π–π stacking, S–π interactions and hydrogen bonding. In addition, all metal ions significantly contributed for stabilizing the architecture via coordination with host and guest molecules. We also studied the thermogravimetric analysis, dipole moment and energy gap between frontier molecular orbitals of 3.

Combination of ionic organic donor and acceptor to form crystalline salt can be an interesting strategy to obtain new types of organic semiconductors, since charge transfer (CT) excitonic properties are anticipated. We have previously achieved a novel CT salt from deprotonated 1,3-(bisdicyanomethylidene)indan anion (TCNIH-) and methyl viologen cation (MV2+) in a 2:1 composition. In this study, the n-alkyl chain length in viologen was systematically changed to find out the border for the evolution of CT character of the mixed salts. [1] Propyl to hexyl viologens (PrV to HxV) were synthesized by quaternization of 4,4’-bipyridine using the corresponding 1-haloalkanes in the yields of 60-62%, whereas methyl, ethyl, heptyl and octyl viologens (MV, EV, HpV, OV) were commercially available. Co-crystals with TCNIH- were precipitated by mixing with viologens at 2 : 1 ratio in water, filtrated and recrystallized from ethanolic solutions. While their crystal structures were examined on powder samples and single crystals, their optical properties were studied by measuring UV-vis and photoluminescence (PL) spectra for CT excitation. Co-crystals with TCNIH- were obtained for all viologens in a 2:1 ratio in the yields of 39-44%. While Na+ salt with TCNIH- preserves the character of the deprotonated TCNIH- in solution, showing a peak at around 590 nm and its absorption extending up to around 850 nm, those with RV2+ having short alkyl chains exhibit absorption towards NIR range and concomitant decrease of visible absorption, due to CT from TCNIH- to RV2+ (Fig. 1). A clear border can be found between PnV and HxV, as the CT absorption is significantly decreased when R is longer than Hx. Crystal structures of the mixed salts were identified as monoclinic for MV, BV, HxV salts, while triclinic for the others. The powder XRD data as well as melting points determined by differential scanning calorimetry indicated significant enlargement of donor-acceptor distances, decrease of melting point, and thereby weakened interaction to account for the observed CT characters. Coulombic interaction between donor and acceptor result in close packing of these co-crystals for their CT characters, whereas it is hindered when alkyl chains longer than Hx is introduced. However, PL from CT states was observed for all the compounds, as the salts with HxV, HpV and OV also showed clearly longer emission than that of Na salt, indicating primary excitation confined in TCNIH-, followed by its relaxation down to the CT states in such salts. Reference [1] E. Saito, et al., ECS Trans., 2018, 88, 301-311 Figure 1

Renal and bone marrow involvements in sarcoidosis are rare. We experienced the case of a 67-year-old man with systemic sarcoidosis, with bone marrow involvement, hepatic involvement and a unique constellation of renal lesion with cellular crescent formation. Immunosuppressive therapy was helpful for maintaining the stability of his pancytopenia, hepatic function and renal function. To the best of our knowledge, the association between sarcoidosis, bone marrow involvement and crescentic glomerulonephritis has been reported in only few cases in literature.

The aim of the present study was to clarify the role of autophagy in cisplatin (CDDP) sensitivity in OCCCs and the role of Beclin 1 in OCCC progression. Autophagy was measured using: i) western blot analysis of LC3 and p62 and ii) microscopic observation of GFP-LC3 puncta. Autophagy was suppressed using chloroquine and Beclin 1 siRNA. Surgical specimens were examined for Beclin 1 protein expression by immunohistochemistry. The correlations between the loss of Beclin 1 expression and clinicopathological characteristics, prognosis and chemosensitivity were investigated. Inhibition of autophagy by chloroquine or Beclin 1 siRNA did not enhance the sensitivity of the ES2 and TOV-21G OCCC cell lines to CDDP. Loss of Beclin 1 expression was observed in 38.3% (23/60) of the analyzed tumors. There was no significant correlation between loss of Beclin 1 expression and FIGO stage, CA125 levels, patient age, status of endometriosis, Ki-67 labeling index, chemotherapy regimen or status of residual tumor. However, negative expression of Beclin 1 was associated with a shorter progression-free survival in comparison to positive Beclin 1 expression in OCCC who received cytoreductive surgery, followed by a standard platinum-based chemotherapy regimen (P=0.027, log-rank test). Beclin 1-negative tumors were no more resistant to primary adjuvant chemotherapy than were Beclin 1-positive tumors (50.0 vs. 66.7%, P=0.937). Beclin 1 knockdown using siRNA increased cell growth but not cell migration and invasion in ES2 and TOV-21G OCCC cell lines. Autophagy defects caused by loss of Beclin 1 are not related to chemoresistance and metastasis, but may be associated with malignant phenotype and poor prognosis of OCCC.

Interactions of supramolecular assemblies constructed from calixarenes or thiacalixarenes and their derivatives with single metal coordination are well studied. But we report here the assembly of p-sulfonatothiacalix[4]arene with two different alkali metals, Na and K, which has been characterized crystallographically. The X-ray crystal structure of Na2K4[p-sulfonatothiacalix[4]arene]·7H2O (5) showed direct evidence for several fascinating interactions in supramolecular chemistry. We also investigated the CO2 gas adsorption properties of complex 5.

Microwave endometrial ablation (MEA) is effective for the emergency control of uterine hemorrhage. However, to the best of our knowledge, there has been only a single report of life-threatening hemorrhage induced by endometrial carcinoma that was treated with MEA. The present report evaluates the efficacy of MEA as an emergency therapeutic option for the control of bleeding due to advanced endometrial carcinoma and minimally-invasive, early-stage endometrial carcinoma in 3 patients. MEA was able to effectively control massive uterine bleeding due to endometrial carcinoma in 2 patients with advanced disease and was curative in a patient with minimally-invasive endometrial carcinoma. Given its safety, simplicity and effectiveness, MEA may be utilized for the emergency treatment of uterine bleeding in advanced endometrial carcinoma, and may be used as a curative treatment in early-stage endometrial carcinoma.

In this study, we examined the clinical significance of KRAS and MAPK1 amplification and assessed whether these amplified genes were potential therapeutic targets in type II ovarian carcinoma. Using fluorescence in situ hybridization, immunohistochemistry, and retrospectively collected clinical data, KRAS and MAPK1 amplifications were identified in 9 (13.2%) and 5 (7.4%) of 68 type II ovarian carcinoma tissue samples, respectively. Interestingly, co-amplification of KRAS and MAPK1 seemed to be absent in the type II ovarian carcinomas tested, except one case. Active phospho-ERK1/2 was identified in 26 (38.2%) out of 68 type II ovarian carcinomas and did not correlate with KRAS or MAPK1 amplification. There was no significant relationship between KRAS amplification and overall or progression-free survival in patients with type II ovarian carcinoma. However, patients with MAPK1 amplification had significantly poorer progression-free survival than patients without MAPK1 amplification. Moreover, type II ovarian carcinoma cells with concomitant KRAS amplification and mutation exhibited dramatic growth reduction following treatment with the MEK inhibitor PD0325901. These findings indicate that KRAS/MAPK1 amplification is critical for the growth of a subset of type II ovarian carcinomas. Additionally, RAS/RAF/MEK/ERK pathway-targeted therapy may benefit selected patients with type II ovarian carcinoma harboring KRAS/MAPK1 amplifications.

Ovarian cancer treatment presently does not reflect molecular differences in histologic subtype. Ovarian clear cell carcinoma (OCCC) exhibits several differences in terms of molecular pathogenesis and tumor behavior from the more common, chemosensitive, serous carcinomas, which makes OCCC a candidate for targeted therapies. A 53-year-old Japanese woman was diagnosed with stage IIIc ovarian clear cell adenocarcinoma with marked chemoresistance to conventional regimens. She demonstrated a partial response to a multikinase inhibitor. The tumor was resistant to PI3K/mTOR pathway inhibitors despite harboring a PIK3CA mutation. The present case suggests a role for targeted therapies in the treatment of OCCC and a need for the identification of biomarkers that will predict response to targeted therapies.

Ovarian low-grade serous carcinoma is thought to begin as a serous cystadenoma or adenofibroma that progresses in a slow stepwise fashion. Among the low-grade serous carcinomas, there is a high frequency of activating mutations in the KRAS or BRAF genes; however, it remains unclear as to how these mutations contribute to tumor progression. This is the first report to track the histopathological progression of serous adenofibroma to low-grade serous carcinoma. Each stage was individually analyzed by pathological and molecular genetic methods to determine what differences occur between the distinct stages of progression.

We aimed to evaluate the prognostic significance of high pre-treatment plasma D-dimer levels in patients with cervical carcinoma (CC) after adjusting for venous thromboembolism.Relationships between the clinicopathological characteristics and the overall (OS) and progression-free (PFS) survival rates of patients with CC (N=129) were examined. Survival was calculated using the Kaplan-Meier method and prognostic indicators assessed using a Cox proportional hazards model.A high pre-treatment plasma level of D-dimers, detected in 42.6% of cases (N=55), was associated with advanced tumour stage. In the multivariate analysis, high pre-treatment plasma D-dimer levels, tumour stage, histological type, and carcinoembryonic antigen (CEA) levels were identified as independent prognostic factors for OS, while tumour stage and CEA levels were identified as independent prognostic factors for PFS.A high pre-treatment plasma level of D-dimers represents an independent prognostic biomarker for CC that could assist in identifying high-risk populations for treatment decisions.

Background: This study examined the clinical significance of NAC1 and the expression level of its potential downstream target fatty acid synthase (FASN) in ovarian clear cell carcinomas (OCCCs), and evaluated the NAC1/FASN pathway as a potential therapeutic target. Methods: NAC1 and FASN expression and NACC1 gene amplification were assessed in ovarian cancers by immunohistochemistry, fluorescence in situ hybridisation, and clinical data collected by a retrospective chart review. C75, a FASN inhibitor, was used to assess whether this pathway represented a therapeutic target in OCCC. Results: High NAC1 expression was most frequent in clear cell tumours (40.0%:24/60). NACC1 gene amplification was identified in none of the 58 OCCCs. The frequency of NACC1 gene amplification was significantly higher in the high-grade serous histology than in the clear cell histology (P

Recently, the ARID1A gene has been identified as a novel tumor suppressor in ovarian clear cell carcinoma. The prognostic significance of the loss of ARID1A expression is not known. The current study was designed to evaluate whether ARID1A was a prognostic factor for progression, survival, and chemoresistance in ovarian clear cell carcinoma. A total of 60 patients, who were surgically treated for primary ovarian clear cell adenocarcinoma, were enrolled. Surgical specimens were examined for ARID1A protein expression by immunohistochemistry. The correlations between the loss of ARID1A expression and clinicopathological characteristics, prognosis, and chemosensitivity were investigated. Loss of ARID1A expression was identified in 9 (15.0%) of 60 ovarian clear cell carcinoma samples. Loss of ARID1A staining intensity (0+) was more frequently found in cells of clear cell carcinomas than in high-grade serous carcinomas (P

[Introduction] Organic charge transfer crystals (CTCs) can be interesting candidates as light absorbers of solar cells to eliminate large voltage loss inherent in dye-sensitized and bulk hetero junction types, in which carrier generation relies on the energy cascades. We have synthesized novel CTCs by forming salts between 1,3-bis(dicyanomethylidene)indan anion (TCNIH-) as a donor and viologen cations as acceptors, namely, N,N’-alkyl substituted 4,4’-bipyridiniums (Fig. 1, methyl = MV2+, ethyl = EV2+, heptyl = HV2+ and octyl = OV2+). [Experimental] Mixed salts of TCNIH- and viologens were obtained by slowly evaporating solvent at room temperature from their 2 : 1 mixed solution in ethanol. While their crystal structures were examined on powder samples and single crystals, their optical properties were studied by measuring UV-Vis and PL spectra between 77 and 298 K on a Horiba Fluorolog-3 equipped with a liq. N2 cryostat. [Results and Discussion] Colorless TCNIH2 turns into deep blue in ethanol due to deprotonation from its methylene carbon to become TCNIH- anion (Fig. 1). While its salt with Na+ was purplish black, having similar absorption features as the solution of TCNIH- with its onset around 800 nm, co-crystals with MV2+ and EV2+ were black with metallic shine to exhibit extended CT absorption in NIR up to ca. 1,000 nm (Fig. 2). On the other hand, those with HV2+ and OV2+ are quite similar to the Na+ salt with only small extension. All of the mixed crystals exhibited XRD patterns different from those of original TCNIH2 and viologen halides, indicating formation of their salts. Single crystal XRD structural analysis performed on large grains revealed monoclinic structure for MV2+ salt, while triclinic for the rest, in which TCNIH- and viologen cations are alternately stacked in 2 : 1 ratio. On increasing the length of the alkyl substituents, expansion and distortion of lattice occurs as seen from their lattice constants summarized in Table 1. The close packing of TCNIH- and MV2+/EV2+ by coulombic interaction obviously contributed to the enhancement of CT, whereas bulky HV2+ and OV2+ prohibited their intimate interaction. PL spectra were measured for the salts (Fig. 3). The Na+ salt indicates a spectrum very similar to that of the TCNIH- solution with not much enhancement and peak shift between 77 and 298 K, indicating emission from the exciton localized in a single TCNIH-. The salts with MV2+ and EV2+ exhibit broad emissions in the NIR range, which are greatly enhanced and resolved into two peaks at 77 K. Exciton-phonon coupling to delocalize exciton within CTCs explains these observations. PL spectra of HV2+ and OV2+ salts are unique, with their energy clearly smaller than that of the Na+ salt, despite of their very similar energy of excitation. Also, clear enhancement and resolution into two peaks at 77 K in case of OV2+ salt suggest relaxation of the TCNIH- localized exciton down to the CT states within these crystals. Acknowledgment The present work was supported by Program for Advancing Strategic International Networks to Accelerate the Circulation of Talented Researchers, “Advanced Next Generation Energy Leadership (R2601, FY2014-2016)” of Japan Society for the Promotion of Science (JSPS). Figure 1

A prospective 1-year study showed that fall incidence was 50% in women with rheumatoid arthritis. Multivariate analysis identified swollen joint count, use of antihypertensives or diuretics, one-leg standing time, and sway area measured by stabilometer as significant parameters associated with falls.Patients with rheumatoid arthritis (RA) may be at increased risk of falling because they frequently experience muscle weakness and stiff or painful joints. The aim of this study was to use a prospective design to determine the incidence of falls and their risk factors in women with RA.Eighty-four women aged 50 and over who had RA were enrolled. The mean age was 64.1 years. We evaluated postural stability, physical performance related to falls, disease activity, muscle volume, and bone density. The occurrence of falls was assessed every month for 1 year. Among 84 patients, 80 completed a 1-year observation.Forty patients (50.0%) reported one or more falls, and two of them (5.0%) had fractures during the follow-up period. The fall group had more swollen joints and took more antihypertensives and/or diuretics. The fall group also had lower postural stability and tended to have reduced physical performance. The one-leg standing time was shorter, and the step-up-and-down test score was lower in the fall group. The sway area was larger in the fall group.Multiple logistic regression analysis identified that number of swollen joints, use of antihypertensives or diuretics, shorter time standing on one foot, and the sway area were the most significant parameters associated with falls.We concluded that fall rates in RA patients were higher than in the general population and that balance impairment or side effects of drugs may play a role in increasing the risk of falls.

The crystal structures of a pair of diastereomeric 1:2 salts of (R)- and (S)-2-methylpiperazine with (2S,3S)-tartaric acid, namely (R)-2-methylpiperazinediium bis[hydrogen (2S,3S)-tartrate] monohydrate, (I), and (S)-2-methylpiperazinediium bis[hydrogen (2S,3S)-tartrate] monohydrate, (II), both C(5)H(14)N(2)(2+).2C(4)H(5)O(6)(-).H(2)O, each reveal the formation of well-defined head-to-tail-connected hydrogen tartrate chains; these chains are linked into a two-dimensional sheet via intermolecular hydrogen bonds involving hydroxy groups and water molecules, resulting in a layer structure. The (R)-2-methylpiperazinediium ions lie between the hydrogen tartrate layers in the most stable equatorial conformation in (I), whereas in (II), these ions are in an unstable axial position inside the more interconnected layers and form a larger number of intermolecular hydrogen bonds than are observed in (I).

Two longitudinal transmitted waves, fast and slow waves, were observed by employing a new quantitative ultrasound (QUS) method. The trabecular bone measurements generated by this method reflect three-dimensional structural information, and the new QUS parameters were able to identify vertebral fractures. The aims were to identify new quantitative ultrasound (QUS) parameters that based on new QUS method reflecting not only bone volume but also the microstructures of trabecular bone ex vivo and to observe how much they predict fracture risk in vivo. Ex vivo measurement: Three human femoral heads were used for the experiment. Attenuation of the slow wave, attenuation of the fast wave, speed of the slow wave, speed of the fast wave (SOFW), bone mass density of trabecular bone, and elastic modulus of the trabecular bone (EMTb) of each specimen were obtained using a new QUS method and compared with three-dimensional structural parameters measured by micro-computed tomography. In vivo measurement: Eighty-nine volunteers were enrolled, and the bone status in the distal radius was measured using a new QUS method. These parameters were compared with data evaluated by peripheral quantitative computed tomography and dual X-ray absorptiometry. Ex vivo measurement: SOFW and EMTb showed correlations with the parameter of trabecular anisotropy. In vivo measurement: The new QUS parameters were able to identify vertebral fractures. The newly developed QUS technique reflects the three-dimensional structure and is a promising method to evaluate fracture risk.

当院は約30万人の医療圏である鳥取県西部地域に位置している．大腿骨近位部骨折地域連携は，当初，急性期病院1施設，回復期リハ病院5施設で開始した．その後参加施設が増加し，平成19年9月現在の参加施設は急性期病院5施設，回復期リハ病院8施設に至っている．平成18年7月に第1回地域連携パス運用連絡会を開催し，以後4ヶ月に1回程度，当院で連絡会を定期的に行っている．当院の連携パスでは人工骨頭置換術後の全入院期間を術後8週，骨接合術後を10週間としている．急性期病院の入院期間はいずれの術式でも1-2週間としており，転院基準は歩行能力に関わらず術後合併症がないこととした．この連携パスは鳥取県西部地域の急性期および連携病院全てで同一のものを使用している．地域連携パス運用例は現在まで5例（人工骨頭2例，骨接合3例）あり，平均在院日数は23日であった．地域で共通の連携パスを積極的に利用し，在宅復帰に繋げていくことが必要と思われた．

The conformational behaviors of all four stereoisomers [5(rctt), 5(rcct), 5(rtct), and 5(rccc)] of tetra-O-methylsulfinylcalix[4]arene were studied by the 1H NMR spectroscopic method. Variable-temperature (VT) NMR experiments of 5(rctt), 5(rcct), and 5(rtct) revealed that each compound adopted the same conformation as that in the crystals at low temperatures and exhibited a self-exchange between the two equivalent species of this conformation at elevated temperatures. The values of the activation enthalpy DeltaH for the self-exchange were similar (approximately 70 kJ mol-1). Further, the activation entropy DeltaS++ was more important for 5(rtct) (-40 J mol-1 K-1) than for 5(rctt) (-5 J mol-1 K-1) and 5(rcct) (-7 J mol-1 K-1); consequently, the exchange rate of 5(rtct) was 150-180 times less than that of the other isomers at 273 K. On the other hand, 5(rccc) was in an equilibrium state between cone and partial-cone conformers at 253 K with the molar ratio being 85:15, which was in reasonable agreement with the relative stability between the two conformers calculated by the ab initio molecular orbital method.

Nucleus accumbens-1 (NAC1), a nuclear factor belonging to the bric-a-brac-tramtrack-broad complex/pox virus and zinc finger gene family, is known to serve important roles in the proliferation and growth of tumor cells, and in chemotherapy resistance. However, the underlying molecular mechanisms through which NAC1 contributes to drug resistance remain unclear. In the present study, the role of NAC1 in drug resistance in ovarian cancer was investigated. NAC1 expression was markedly negatively associated with growth arrest and DNA-damage-inducible 45γ-interacting protein 1 (GADD45GIP1) expression in ovarian cancer. Increased NAC1 expression or decreased GADD45GIP1 expression was significantly associated with decreased progression-free survival (P=0.0041). Multivariate analysis demonstrated that NAC1/GADD45GIP1 expression was an independent prognostic factor of progression-free survival (P=0.0405). It was investigated whether cellular senescence was involved in NAC1-mediated resistance to cisplatin, a commonly used chemotherapeutic drug in the treatment of ovarian cancer. Treatment with cisplatin activated cellular senescence in ovarian cancer cell lines (SKOV3 and TOV-21G cells). Furthermore, knockdown of NAC1 by RNA interference significantly increased GADD45GIP1 expression and inhibited cisplatin-induced cellular senescence, resulting in increased cisplatin cytotoxicity in SKOV3 cells, which express increased levels of NAC1. To investigate whether the sensitizing effect of NAC1 inhibition on cisplatin-induced cytotoxicity may be attributed to the suppression of cellular senescence, the effects of NAC1 overexpression were assessed in TOV-21G cells, which do not express endogenous NAC1. Transfection with NAC1 in TOV-21G cells reduced the sensitivity of TOV-21G cells to cisplatin, indicating that suppression of cellular senescence was induced by GADD45GP1 activation. The results of the present study suggest that NAC1 is a negative regulator of cellular senescence and that NAC1-dependent suppression of senescence, mediated through GADD45GIP1, serves an important role in promoting cisplatin resistance. Therefore, the NAC1/GADD45GIP1 axis may be a potential target for the treatment of ovarian cancer, particularly in platinum-resistant cancers.

It is very rare that ovarian carcinoma metastasizes to the pancreas, and pathological diagnosis is required to confirm the primary site. The present study reported a 73-year-old woman with serous carcinoma of the ovary that metastasized to the tail of the pancreas. Metastasis was confirmed by pathological and immunohistochemical examination of a biopsy of the ovarian tumor, an endoscopic ultrasound-guided fine-needle aspiration biopsy of the pancreatic tumor and computerized tomography-guided paraaortic lymph node biopsy. A biopsy of the ovarian tumor is useful to make a precise diagnosis and to determine proper treatment when ovarian and pancreatic tumors are identified at the same time and the primary neoplasm is uncertain.

Background Uterine arteriovenous malformation is a rare but life-threatening condition that accounts for 1–2% of massive vaginal bleeding. Uterine arteriovenous malformations are less common after menopause. The condition can be diagnosed using Doppler ultrasound, magnetic resonance imaging, computed tomography, and pelvic angiography. Case presentation We report a postmenopausal patient with a uterine arteriovenous malformation who underwent emergency hysterectomy for sudden onset of life-threatening uterine bleeding following an initially successful but ultimately failed uterine artery embolization. Interestingly, it was not difficult to ligate and cut the dilated vessels and we were able to safely perform the hysterectomy with little bleeding in the operative field. The hysterectomy was successful, with most of the intraoperative vaginal blood loss due to the ruptured arteriovenous malformation. One year after surgery, the patient has had no vaginal bleeding. Conclusion We consider hysterectomy to be a comparatively safe and effective therapeutic option for postmenopausal women who suffered from uterine arteriovenous malformations with life-threatening uterine bleeding.

We measured the environmental glutaraldehyde (GA) levels during the disinfection of endoscopes and also investigated the subjective symptoms of the workers engaged in that work. At 6 hospitals in the Tokyo and Kanagawa area, 8 rooms for endoscope washing and disinfecting the endoscopy equipment were surveyed. The geometric mean environmental GA levels in the 8 rooms were 1.3 to 19.6 ppb. The personal exposure levels at the time of replacing the antiseptic solution containing GA in two of the disinfecting rooms were 94.2 and 84.9 ppb. Subjective symptoms such as ophthalmic, nasal, respiratory, pharyngeal symptoms and nausea were more prevalent among workers than controls as evidenced from the questionnaire survey.

All four stereoisomers of p-tert-butylsulfinylcalix[4]arene [4(rccc), 4(rcct), 4(rctt), and 4(rtct)], arising from the disposition of the four sulfinyl groups with respect to the mean plane of the four bridging sulfur atoms, have been prepared via oxidation of p-tert-butylthiacalix[4]arene (2) or its tetra-O-benzyl ethers 5 of defined conformations. Thus, treatment of 2 with 4.4 molar equiv of NaBO3·4H2O gave the rtct and rctt isomers in 27% and 17% yields, respectively, while oxidation of cone 5 (5C) and partial cone 5 (5PC) proceeded stereoselectively to give, after debenzylation of the resulting tetrasulfoxides 12 and 15, the rccc and rcct isomers in 56% and 28% yields, respectively, based on 5. The sulfinylcalix[4]arenes 4 were treated with iodomethane in the presence of a base to give the corresponding tetramethyl ethers 16, the structures of which in regard to the disposition of the sulfinyl groups and the conformation of the phenol units were determined by X-ray crystallography. Also reported is th...

An enantioresolution of 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl oxide (BINAPO) into its enantiomers was achieved using the inclusion complex with a commerciallyavailable chiral 2,2'-dihydroxy-1,1'-binaphthyl ((R)-BINOL), giving the two enantiomers with 99% ee and 72% ee, respectively.

(Purpose) It is well known that lumbar bone mineral density is high in spondylosis deformans. We examined the relationship between change in spondylosis and general bone mineral density. (Subjects and Methods) The subjects of our investigation consisted of 90 women (average 46.4 years) around post menopouse. We examined A-P X-ray of their lumbar spine and measured bone mineral density of the lumbar spine, radius, and calcaneous. The deformed degree of the lumbar spine indicated bone spur (from L1 to L5 vertebral body), and we compared these three parts using the total estimated value of five stages (0-4) with Nathan classifications. For bone mineral density, we examined relationship with the degree of lumbar spinal deformity by using Z-score. (Results) We divided the patients into two groups: H group and L group. The H group scored above 4 points with the Nathan classification, and the L group below 4 points. The bone mineral density of all three parts was highly significant (P