Toward Increasing Micropore Volume between Hybrid Layered Perovskites with Silsesquioxane Interlayers.

Hybrid organic-inorganic layered perovskites are typically nonporous solids. However, the incorporation of silsesquioxanes with a cubic cage structure as interlayer materials creates micropores between the perovskite layers. In this study, we increase in the micropore volume in layered perovskites by replacing a portion of the silsesquioxane interlayers with organic amines. In the proposed method, approximately 20% of the silsesquioxane interlayers can be replaced without changing the layer distance owing to the size of the silsesquioxane. When small amines (e.g., ethylamine) are used in this manner, the micropore volume of the obtained hybrid layered perovskites increases by as much as 44%; when large amines (e.g., phenethylamine) are used, their micropore volume decreases by as much as 43%. Through the variation of amine fraction, the micropore volume can be adjusted in the range. Finally, the magnetic moment measurements reveal that the layered perovskites with mixed interlayers exhibit ferromagnetic ordering at temperature below 20 K, thus indicating that the obtained perovskites maintain their functions as layered perovskites.

Left ventricular end-diastolic dimension and septal e' are predictors of cardiac index at rest, while tricuspid annular plane systolic excursion is a predictor of peak oxygen uptake in patients with pulmonary hypertension.

Little is known regarding a correlation of hemodynamics at rest or exercise capacity with echocardiographic parameters in patients with pulmonary hypertension (PH). To clarify these potential correlations, we performed transthoracic echocardiography, right heart catheterization, and cardiopulmonary exercise testing in 53 patients with pulmonary arterial hypertension (PAH) and chronic thromboembolic pulmonary hypertension (CTEPH). Left ventricular end-diastolic dimension (LVDd), early diastolic velocity of the septal mitral annulus (septal e'), tricuspid regurgitation peak gradient (TRPG), and tricuspid annular plane systolic excursion (TAPSE) were significantly correlated with cardiac index (LVDd; r = 0.477, P < 0.001, septal e'; r = 0.463, P = 0.001, TRPG; r = - 0.455, P = 0.001 and TAPSE; r = 0.406, P = 0.003, respectively). Multiple regression analysis revealed that LVDd and septal e' were significantly associated with cardiac index (CI) and stroke volume index at rest. Among the exercise capacity markers evaluated, TAPSE, TRPG, and LVDd were significantly correlated with peak oxygen uptake (TAPSE; r = 0.534, P < 0.001, TRPG; r = - 0.466, P = 0.001 and LVDd; r = 0.411, P = 0.002, respectively). Multiple regression analysis showed that TAPSE was significantly associated with peak oxygen uptake (VO2). In PAH and CTEPH patients, LVDd and septal e' were significantly associated with CI at rest, whereas TAPSE was significantly associated with peak VO2. Echocardiographic parameters may predict the prognostic factors of PAH and CTEPH patients.

Usefulness of scoring right ventricular function for assessment of prognostic factors in patients with chronic thromboembolic pulmonary hypertension.

Right ventricular (RV) function is associated with prognosis in chronic thromboembolic pulmonary hypertension (CTEPH). This study aimed to establish an RV dysfunction score using RV echocardiographic parameters to clarify the clinical characteristics in patients with CTEPH and to compare RV dysfunction score with parameters such as World Health Organization (WHO) functional class, hemodynamics, exercise capacity, and plasma BNP level. We enrolled 35 inpatients with CTEPH (mean age, 62 ± 15 years, 15 males). We constructed 'an RV dysfunction score' calculated as the summation of each point awarded for the presence of four parameters: tricuspid annular plane systolic excursion (TAPSE) < 16 mm, 1 point; tissue Doppler-derived tricuspid lateral annular systolic velocity (S') < 10 cm/s, 1 point; right ventricular fractional area change (RVFAC) < 35%, 1 point; and right ventricular myocardial performance index (RV-MPI) > 0.4, 1 point. TAPSE, S', RVFAC, and RV-MPI was 18.7 ± 4.8 mm, 11.9 ± 3.1 cm/s, 33.5 ± 13.9%, and 0.39 ± 0.2, respectively. The RV dysfunction score was associated with symptom [WHO functional class (p = 0.026)], hemodynamics [mean PAP (p = 0.01), cardiac index (p = 0.009), pulmonary vascular resistance (p = 0.001), and SvO2 (p = 0.039)], exercise capacity [6-min walk distance (p = 0.046), peakVO2 (p = 0.016), and VE/VCO2 slope (p = 0.031)], and plasma BNP level (p = 0.005). This RV dysfunction score using the four RV echocardiographic parameters could be a simple and useful scoring system to evaluate prognostic factors in patients with CTEPH.

Hybrid Lead Halide Layered Perovskites with Silsesquioxane Interlayers.

Hybrid organic-lead halide perovskites exhibit remarkable properties as semiconductors and light absorbers. Here, we report the formation of silsesquioxane-lead halide hybrid layered perovskites. We prepared silsesquioxane with a cubic cage-like structure and fabricated hybrid silsesquioxane-lead halide layered perovskites in a self-assembled manner. It is demonstrated that the silsesquioxane maintain their cage-like structure between lead halide perovskite layers. The silsesquioxane-lead halide perovskites also show excitonic absorption and emission in the visible light region similar to typical lead halide layered perovskites.

Cardiopulmonary Exercise Testing as a Tool for Diagnosing Pulmonary Hypertension in Patients with Dilated Cardiomyopathy.

BACKGROUND: Recently, it has become increasingly recognized that pulmonary hypertension (PH) is a particularly threatening result of left-sided heart disease. However, there have been few investigations of the impact of cardiopulmonary exercise testing (CPX) variables on PH in dilated cardiomyopathy (DCM). We evaluated the usefulness of crucial CPX variables for detecting elevated pulmonary arterial pressure (PAP) in patients with DCM. METHODS: Ninety subjects with DCM underwent cardiac catheterization and CPX at our hospital. Receiver operator characteristic (ROC) analysis was performed to assess the ability of CPX variables to distinguish between the presence and absence of PH. RESULTS: Overall mean values were: mean PAP (mPAP), 18.0 ± 9.6 mmHg; plasma brain natriuretic peptide, 233 ± 295 pg/mL; and left ventricular ejection fraction, 30.2 ± 11.0%. Patients were allocated to one of two groups on the basis of mean PAP, namely DCM without PH [mean PAP (mPAP) <25 mmHg; n = 75] and DCM with PH (mPAP ≥25 mmHg; n = 15). A cutoff achieved percentage of predicted peak VO2 (%PPeak VO2 ) of 52.5% was the best predictor of an mPAP ≥25 mmHg in the ROC analysis (area under curve: 0.911). In the multivariate analysis, %PPeak VO2 was the only significant independent predictor of PH (Wald 6.52, odds ratio 0.892, 95% CI 0.818-0.974; P = 0.011). CONCLUSIONS: %PPeak VO2 was strongly associated with the presence of PH in patients with DCM. Taken together, these findings indicate that CPX variables could be important for diagnosing PH in patients with DCM.

Layered hybrid perovskites with micropores created by alkylammonium functional silsesquioxane interlayers.

Layered organic-inorganic hybrid perovskites that consist of metal halides and organic interlayers are a class of low-dimensional materials. Here, we report the fabrication of layered hybrid perovskites using metal halides and silsesquioxane with a cage-like structure. We used a silsesquioxane as an interlayer to produce a rigid structure and improve the functionality of perovskite layers. Propylammonium-functionalized silsesquioxane and metal halide salts (CuCl2, PdCl2, PbCl2, and MnCl2) were self-assembled to form rigid layered perovskite structures with high crystallinity. The rigid silsesquioxane structure produces micropores between the perovskite layers that can potentially be filled with different molecules to tune the dielectric constants of the interlayers. The obtained silsesquioxane-metal halide hybrid perovskites exhibit some characteristic properties of layered perovskites including magnetic ordering (CuCl4(2-) and MnCl4(2-)) and excitonic absorption/emission (PbCl4(2-)). Our results indicate that inserting silsesquioxane interlayers into hybrid perovskites retains and enhances the low-dimensional properties of the materials.

Controlled formation of silica structures using siloxane/block copolymer complexes prepared in various solvent mixtures.

Block copolymers exhibit regularly patterned structures induced by microphase separation. Here we present a method for preparing various particulate silica (SiO2) nanostructures by controlling the microphase separation of block copolymers. In this method, siloxane, a SiO2 precursor, is adsorbed onto poly(4-vinylpyridine) blocks of polystyrene-block-poly(4-vinylpyridine) in solvent mixtures. After siloxane/polymer complexes are coprecipitated via further siloxane polycondensation, the resulting precipitates are heated to remove the polymer. The results of scanning electron microscopy revealed that SiO2 formed various structures including cylindrical, spherical, and lamellar. Different SiO2 nanostructures formed via the microphase separation of siloxane/polymer complexes are prepared simply by varying solvent mixtures without changing the polymer chain. The structural change is interpreted in terms of polymer-solvent interactions and volume fractions in siloxane/polymer complexes.

A working hypothesis for broadening framework types of zeolites in seed-assisted synthesis without organic structure-directing agent.

Recent research has demonstrated a new synthesis route to useful zeolites such as beta, RUB-13, and ZSM-12 via seed-assisted, organic structure-directing agent (OSDA)-free synthesis, although it had been believed that these zeolites could be essentially synthesized with OSDAs. These zeolites are obtained by adding seeds to the gels that otherwise yield other zeolites; however, the underlying crystallization mechanism has not been fully understood yet. Without any strategy, it is unavoidable to employ a trial-and-error procedure for broadening zeolite types by using this synthesis method. In this study, the effect of zeolite seeds with different framework structures is investigated to understand the crystallization mechanism of zeolites obtained by the seed-assisted, OSDA-free synthesis method. It has been found that the key factor in the successful synthesis of zeolites in the absence of OSDA is the common composite building unit contained both in the seeds and in the zeolite obtained from the gel after heating without seeds. A new working hypothesis for broadening zeolite types by the seed-assisted synthesis without OSDA is proposed on the basis of the findings of the common composite building units in zeolites. This hypothesis enables us to design the synthesis condition of target zeolites. The validity of the hypothesis is experimentally tested and verified by synthesizing several zeolites including ECR-18 in K-aluminosilicate system.

Dealumination of small-pore zeolites through pore-opening migration process with the aid of pore-filler stabilization.

Small-pore zeolites are gaining increasing attention owing to their superior catalytic performance. Despite being critical for the catalytic activity and lifetime, postsynthetic tuning of bulk Si/Al ratios of small-pore zeolites has not been achieved with well-preserved crystallinity because of the limited mass transfer of aluminum species through narrow micropores. Here, we demonstrate a postsynthetic approach to tune the composition of small-pore zeolites using a previously unexplored strategy named pore-opening migration process (POMP). Acid treatment assisted by stabilization of the zeolite framework by organic cations in pores is proven to be successful for the removal of Al species from zeolite via POMP. Furthermore, the dealuminated AFX zeolite is treated via defect healing, which yields superior hydrothermal stability against severe steam conditions. Our findings could facilitate industrial applications of small-pore zeolites via aluminum content control and defect healing and could elucidate the structural reconstruction and arrangement processes for inorganic microporous materials.

Extrinsic compression of the left main coronary artery: A rare cause of cardiogenic shock.

A left main coronary artery (LMCA) stenosis due to extrinsic compression by mediastinal tumor is a rare finding. In this case reports, we present a 63-year-old woman, who was transferred to the emergency department with chief complains of persistent chest and back pain. An electrocardiogram revealed diffuse ST-segment depression (elevation in lead aVR). Contrast-enhanced computed tomography (CT) showed a huge cystic mass above the left atrium. After the CT examination, she was temporarily in shock. Compression of the LMCA was evident on the CT angiography and a diagnosis of acute myocardial infarction due to compression of the LMCA by a tumor was made. An emergent resection of the tumor was performed. Histopathological assessment of the resected cyst revealed that it was a schwannoma. She made an uneventful postoperative recovery. A follow-up 3-dimensional CT scan performed after the operation confirmed no evidence of LMCA compression.

Goal-Oriented Sequential Combination Therapy Evaluated Using Cardiopulmonary Exercise Parameters for the Treatment of Newly Diagnosed Pulmonary Arterial Hypertension　- Goal-Oriented Therapy Evaluated by Cardiopulmonary Exercise Testing for Pulmonary Arterial Hypertension (GOOD EYE).

Background: Many treatment options are available for pulmonary arterial hypertension (PAH), but specific recommendations for long-term treatment are unavailable. We compared prognosis in PAH patients receiving goal-oriented, sequential combination therapy evaluated using cardiopulmonary exercise testing (CPX) parameters or conventional empiric therapy. Methods and Results: The Goal-Oriented Therapy Evaluated by Cardiopulmonary Exercise Testing for Pulmonary Arterial Hypertension (GOOD EYE) study was a multicenter, retrospective/prospective study in which a total of 129 patients with newly diagnosed PAH were enrolled (goal-oriented sequential combination therapy, n=42; conventional empiric therapy, n=87). Patients in the goal-oriented therapy group received sequential combination therapy, the efficacy of which was regularly evaluated using CPX parameters. Patients in the conventional empiric therapy group received conventional empiric therapy. The primary endpoint was cardiovascular death. In the goal-oriented therapy group, plasma brain natriuretic peptide, mean pulmonary arterial pressure, pulmonary vascular resistance, and 6-min walk test were significantly improved at 12 months compared with baseline. Survival in the goal-oriented therapy group at 1, 2, and 3 years (97.6%, 95.2%, and 86.0%, respectively) tended to be higher than that in the conventional empiric therapy group (P=0.082). Conclusions: Goal-oriented sequential combination therapy evaluated using CPX parameters may be associated with a favorable prognosis compared with conventional empiric therapy in patients with newly diagnosed PAH.

The influence of frailty under direct oral anticoagulant use in patients with atrial fibrillation.

BACKGROUND: Frailty is a prognostic factor in patients with atrial fibrillation (AF). However, there is no report on the associations between frailty and clinical adverse events in patients with AF taking direct oral anticoagulants (DOAC). The factors related to the occurrence of clinical adverse events are still under discussion. Therefore, we examined the associations between frailty and clinical adverse events in patients with AF taking DOAC in daily clinical practice. METHODS: We retrospectively evaluated 240 consecutive patients with AF who had been newly prescribed DOAC in our hospital from April 2016 through May 2017. Data collected included Clinical Frailty Scale (CFS) scores, laboratory results and basic demographic information. RESULTS: During the mean follow-up period of 13.4 months, 20 patients died (7.6 per 100 person-years), stroke or systemic embolism occurred in seven patients (2.6 per 100 person-years) and major bleeding occurred in 11 patients (4.2 per 100 person-years). We defined these adverse events as composite end points, and we estimated adjusted HRs and 95% CIs for risk factors using the Cox proportional hazard regression model. Frailty (defined as a CFS score of 5 or more; HR: 3.71; 95% CI: 1.59 to 8.65), female sex (HR: 3.49; 95% CI: 1.73 to 7.07), serum albumin level (HR: 0.47; 95% CI: 0.28 to 0.79) and malignancy (HR: 4.02; 95% CI: 1.83 to 8.84) were independent predictors of the composite end points. CONCLUSIONS: Frailty, female sex, hypoalbuminaemia and malignancy were associated with clinical adverse events in patients with AF who were prescribed DOAC.

Seed-Assisted Synthesis of MWW-Type Zeolite with Organic Structure-Directing Agent-Free Na-Aluminosilicate Gel System.

The seed-assisted synthesis of zeolites without using organic structure-directing agents (OSDAs) has enabled alternative routes to the simple, environmentally friendly and low-cost production of industrially important zeolites. In this study, the successful seed-assisted synthesis of MCM-22 (MWW-type) zeolite with an OSDA-free gel is reported for the first time. MWW-type zeolites are obtained by the addition of as-synthesized MCM-22 seeds prepared with hexamethyleneimine (HMI) into OSDA-free Na-aluminosilicate gels. Based on the results of XRD, ICP-AES, NMR, N2 physisorption and NH3 -TPD, the product exhibited different features compared to those of the seeds. The H-form product can serve as a catalyst in Friedel-Crafts alkylation reaction of anisole with 1-phenylethanol, and its catalytic activity is comparable to the seeds. Furthermore, XRD, FE-SEM, TG-DTA, CHN, FT-IR and NMR analyses of products and intermediates provide insights into the role of seeds and occluded HMI, the crystallization process, and key factors for achieving seed-assisted synthesis of MWW-type zeolites with an OSDA-free gel system. The present results provide a new perspective for the economical and environmentally friendly production of MWW-type zeolites.

Left main coronary artery compression by a dilated main pulmonary artery and left coronary sinus of Valsalva aneurysm in a patient with heritable pulmonary arterial hypertension and FLNA mutation.

Left main coronary artery (LMCA) disease due to external compression by a dilated main pulmonary artery (MPA) is an uncommon clinical entity. Here, we describe a 52-year-old woman with pulmonary arterial hypertension (PAH) and anteroseptal old myocardial infarction (OMI). The cause of the OMI was external compression of the LMCA by the dilated MPA and aneurysm of the left coronary sinus of Valsalva. The patient's sister (aged 56 years) had also been diagnosed with PAH and both women had a novel heterozygous splicing mutation, IVS2-2A > G (c.374-2A > G in NM_001456), in the filamin A ( FLNA) gene. To our knowledge, this is the first report of HPAH which is likely to be due to FLNA mutation and compression of the LMCA between a dilated MPA and aneurysm of the left coronary sinus of Valsalva.

Circulatory power and ventilatory power over time under goal-oriented sequential combination therapy for pulmonary arterial hypertension.

Many therapeutic options are available for patients with pulmonary arterial hypertension (PAH). However, little is known about the effects of sequential combination therapy on exercise capacity. Here we monitored exercise capacity by cardiopulmonary exercise testing (CPX) and observed the benefit of using a peak VO2 cutoff of 15 mL/kg/min to guide combination therapy. Thirty patients newly diagnosed with PAH were treated with goal-oriented sequential combination therapy. Endothelin receptor antagonists (ERA) were the first-line treatment, with phosphodiesterase type 5 inhibitors (PDE-5i) as the preferred combination partner. The patients underwent cardiac catheterization at baseline and after 12 months and CPX at baseline and after three, six, and 12 months. Circulatory power (CP) was defined as the product of peak O2 uptake and peak systolic blood pressure (SBP); ventilatory power (VP) was defined as peak SBP divided by the minute ventilation-CO2 production slope. After 12 months, ERA had been administered to 100% of the study patients and PDE-5i to 82%. Mean CP at baseline and after three, six, and 12 months was 1807, 2063, 2248, and 2245 mmHg·min/mL/kg, respectively, and mean VP was 2.93, 3.53, 4.16, and 3.68 mmHg, respectively. CP was greater after 6 months than at baseline ( P = 0.047); VP was greater after three months than at baseline ( P = 0.019) and further improved at six months compared with three months ( P = 0.040). Therefore, repeated CPX assessment, including measurement of CP and VP, can provide useful information regarding the efficacy of goal-oriented treatment for PAH.

Effects of bosentan on peripheral endothelial function in patients with pulmonary arterial hypertension or chronic thromboembolic pulmonary hypertension.

Endothelin receptor antagonists (ERAs) have been shown to improve the prognosis of patients with pulmonary arterial hypertension (PAH). However, the effect of the oral dual ERA bosentan on peripheral endothelial dysfunction (PED), as assessed by flow-mediated vasodilation (FMD), in patients with pulmonary hypertension is not well characterized. We investigated the effect of bosentan on PED in patients with PAH or inoperable chronic thromboembolic pulmonary hypertension (CTEPH). A total of 18 patients with PAH and 8 with CTEPH were treated with bosentan. All patients underwent FMD assessment before and after 3 months of bosentan treatment. Whereas FMD increased from 6.01% ± 2.42% at baseline to 8.07% ± 3.18% after 3 months (P < 0.0001) in patients with PAH, those with CTEPH showed no change in FMD after bosentan therapy. In addition, FMD at baseline showed no correlation with pulmonary vascular resistance (r = 0.09) or plasma brain natriuretic peptide levels (r = -0.23) in patients with PAH. Bosentan treatment ameliorated PED in patients with PAH but not in those with inoperable CTEPH. In addition, FMD did not correlate with PAH severity.

Controlled formation of ordered coordination polymeric networks using silsesquioxane building blocks.

In this report, we synthesized ordered coordination polymers using polyhedral oligomeric silsesquioxanes (POSS) as a building block. A POSS with eight carboxylic terminals was coordinated with copper ions at various temperatures, forming polymeric networks. This novel coordination polymer has a long-range ordered structure.

Assessment of respiratory disturbance index determined with a non-restrictive monitor and of autonomic nervous system parameters in heart failure patients: A pilot study.

BACKGROUND: There is a link between sympathetic overactivity and sleep-disordered breathing (SDB), and both of which are important indicators of the development of heart failure. To manage the increasing numbers of heart failure patients, any method used to check for them needs to be as non-invasive, simple, and cost-effective as possible. The purpose of this study is to assess screening of SDB with a non-restrictive monitor and the autonomic nervous system in heart failure patients. METHODS: The subjects were 49 patients (mean age: 67 years; male: 78%) hospitalized for worsening heart failure. After stabilization with appropriate medical therapy, each patient simultaneously underwent sleep apnea syndrome (SAS) screening with the SD-101 (Kenzmedico Co. Ltd., Saitama, Japan), which is a novel, non-restrictive, sheet-like monitor for SAS screening, and assessment of heart rate variability (HRV) with a Holter monitor. In addition, we assessed daytime sleepiness by using the Epworth Sleepiness Scale. RESULTS: The mean respiratory disturbance index (RDI) was 21.9 events/h. Males had significantly greater RDI values than females (24.5±11.2 events/h vs. 13.0±6.2 events/h, p<0.001). RDI on SD-101 testing was closely correlated with cyclic variation of heart rate index obtained with a Holter electrocardiogram scanner (r=0.843). Although plasma brain natriuretic peptide level was not correlated with HRV, plasma norepinephrine level was moderately well correlated with the total low- to high-frequency ratio of HRV (r=0.529). CONCLUSIONS: SAS screening is important for heart failure patients, because absence of subjective sleepiness is not reliable in ruling out SDB. The SAS screening with SD-101 might apply for managing heart failure.

Simple template-free synthesis of high surface area mesoporous ceria and its new use as a potential adsorbent for carbon dioxide capture.

The development of an efficient technique for carbon dioxide (CO2) capture from a variety of large stationary sources is in important global issue. If we are to achieve an energy-efficient and effectively higher CO2 capture process based on an adsorption approach, we need new adsorbent materials realistic enough to provide higher CO2 loading on a volumetric basis. For this reason we have focused on the practical use of high surface area mesoporous ceria as a new application in the field of CO2 capture. In this regard, we demonstrate the simple and inexpensive template-free synthesis of mesoporous ceria with a high surface area up to 200 m(2) g(-1), and characterize it as an effective CO2 adsorbent for the first time. The mesoporous ceria is prepared based on sol-gel chemistry, where the product is simply precipitated by the self-assembly of ceria nanoparticles within a short reaction period at room temperature under highly alkaline conditions with optimized chemical compositions. The results of CO2 adsorption-desorption measurement at 298 K show that the obtained ceria with an enhanced surface area exhibits a noticeably higher CO2 adsorption capacity per volume than commercially available non-porous ceria, activated carbon and zeolite 13X over a wide pressure range with robust stability as well as regenerability. This work enables us to prepare promising new materials for the CO2 capture process based on an easy-to-handle synthesis system, and this effective material will have a broad applicability to the efficient CO2 separation from variety of industrial emission sources. The features of the obtained mesoporous ceria are reported and discussed.

Intravascular ultrasound-guided percutaneous coronary intervention for total occlusion of the proximal left anterior descending artery caused by spontaneous coronary dissection in a young woman.

A 35-year-old woman was admitted to our hospital because of a sudden cardiac arrest caused by an acute anterior myocardial infarction. Emergency coronary angiography showed total occlusion of the proximal left anterior descending artery (LAD). We performed an intravascular ultrasound (IVUS) to detect the LAD orifice and successfully inserted the guidewire to the occluded LAD. An IVUS revealed coronary dissection and no atheromatous plaque from the orifice to the mid-portion of the LAD and the guidewire was in the true lumen. Two bare metal stents were implanted in the proximal and mid portion of the LAD. After stenting to the LAD, coronary dissection retrogradely extended to the left circumflex artery (LCx). Therefore, we performed additional stent implantation from the left main trunk (LMT) to the proximal LCx and the just proximal LAD. An IVUS guided percutaneous coronary intervention (PCI) enabled complete revascularization to spontaneous coronary artery dissection.