The treatment of the bulky Rind-based dibromosilanes, (Rind)SiBr () [Rind = 1,1,7,7-tetra-R-3,3,5,5-tetra-R--hydrindacen-4-yl: EMind (: R = Et, R = Me) and Eind (: R = R = Et)], with two equivalents of BuLi in EtO at low temperatures resulted in the formation of blue solutions derived from the diarylsilylenes, (Rind)Si: (). Upon warming the solutions above -20 °C, the blue color gradually faded, accompanying the decomposition of and yielding cyclic hydrosilanes () via intramolecular C-H bond insertion at the Si(II) center. The molecular structures of the bulky Eind-based and were confirmed by X-ray crystallography.
View Article and Find Full Text PDFThe O splitting mediated by the bulky Rind-based diphosphenes resulted in the clean formation of the mixed-valent diphosphorus compounds, diphosphene oxides, with PO moieties. Their structural features and electronic properties have been clearly characterized by experimental and theoretical methods.
View Article and Find Full Text PDFA series of ()-1,2-diaryldigermenes, (Eind)ArGeGeAr(Eind) [Ar = phenyl (2), thiophen-2-yl (3), 9,9-dimethyl-2-fluorenyl (4) and 2,2'-bithiophen-5-yl (5)], supported by the fused-ring bulky 1,1,3,3,5,5,7,7-octaethyl--hydrindacen-4-yl (Eind) groups, have been obtained as yellow-orange to red crystalline solids by the reaction of 1,2-dibromodigermene, (Eind)BrGeGeBr(Eind) (1), with ArLi. In the crystals of 2-5, the digermene cores show a flexible nature adopting a -bent geometry with the -bent angles () between the Ge-Ge vector and the C-Ge-C plane of 34.04(12)° (2), 38.
View Article and Find Full Text PDFPurpose: The Patient State Index (PSI) is a newly introduced electroencephalogram-based tool for objective and continuous monitoring of sedation levels of patients under general anesthesia. This study investigated the potential correlation between the PSI and the Richmond Agitation‒Sedation Scale (RASS) score in intensive care unit (ICU) patients and established the utility of the PSI in assessing sedation levels.
Methods: In this prospective observational study, PSI values were continuously monitored via SedLine® (Masimo, Irvine, CA, USA); the RASS score was recorded every 2 h for patients on mechanical ventilation.
While the implication of the aromaticity concept has been dramatically expanded to date since its emergence in 1865, the classical [4+2]/4-electron counting protocol still plays an essential role in evaluating the aromatic nature of compounds. Over the last few decades, a variety of heavier heterocycles featuring the formal [4+2] π-electron arrangements have been developed, which allows for assessing their aromatic nature. In this review, we present recent developments of the [4+2]-electron systems of heavier heterocycles involving group 13-15 elements.
View Article and Find Full Text PDFJ Am Chem Soc
July 2021
Dewar benzene, one of the isolable valence isomers of CH, has been extensively studied since its first synthesis in 1962. By contrast, the chemistry of inorganic congeners of Dewar benzene, which can be formally gained by replacing the skeletal carbon atoms with heteroatoms, has been less developed despite their peculiar structural and electronic features. Among them, the extant B,N-Dewar benzenes are limited to the BN system.
View Article and Find Full Text PDFThe Hückel rule defines that monocyclic and planar conjugated systems containing [4 + 2] π electrons are aromatic. Here, the authors highlight boron species that feature a globally 4 π system, defying the Hückel rule, but nonetheless exhibit aromaticity.
View Article and Find Full Text PDFIt has been computationally proposed that there are more than 200 possible isomeric structures for the CH molecule, among which benzene (CH) represents the most thermodynamically stable molecule and its chemistry has been extensively developed. Three benzene valence isomers (CR), namely, prismane, Dewar benzene, and benzvalene, have also been synthesized to date. Incorporation of heteroatoms in the skeletal frameworks allows access to inorganic analogues of benzene and its valence isomers, which have attracted considerable attention due to their peculiar structural and electronic features.
View Article and Find Full Text PDFThe aromatically relevant parameters of boron-rich inorganic benzenes-neutral and dianionic 1,4-diaza-2,3,5,6-tetraborinine derivatives (BNR)-have been computationally estimated and evaluated from geometric, electronic, magnetic, and energetic points of view. The majority of the criteria (ASE, NICS, ELF, and PDI) indicate that the aromaticity of the neutral BN benzene analogue stabilized by Lewis bases lies in between those of benzene and borazine. On the other hand, the aromaticity of the dianionic BN benzene analogue 4' is controversial.
View Article and Find Full Text PDFA neutral 1,4-diaza-2,3,5,6-tetraborinine derivative (3) featuring a 6π ring system has been synthesized and structurally characterized. The prospective aromatic nature of 3 was assessed by single-crystal X-ray analysis, NMR, and UV/Vis absorption spectroscopy as well as computational studies. Furthermore, preliminary reactivity investigations showed that 3 does not only react with diphenyl acetylene but also readily captures CO in a [4+2] cycloaddition under ambient conditions.
View Article and Find Full Text PDFThe reactions of germylone 1 with one equivalent of [M(COD)Cl]2 (M = Ir, Rh) afforded the germylone-bridged bimetallic complexes 2 and 3, which have been spectroscopically and structurally characterized. Density functional theory (DFT) studies reveal the relatively strong interactions between the Ge atom and these metals. By the reaction of [Rh(COD)Cl]2 with CO followed by addition of 1, a complex 4 involving a Rh-Ge-Rh-Ge-Rh chain was also synthesized.
View Article and Find Full Text PDFJ Am Chem Soc
September 2018
Despite the large number of plausible isomers of benzene (CH), only four valence isomers [(CH)] have been experimentally detected, all of which are nonionic and possess skeletal frameworks built from localized C-C bonds. Herein, we present the isolation of a diazatetraborabenzene analogue of a hypothetical zwitterionic valence isomer of benzene. Therein, two electrons are delocalized over the four boron atoms in the six-membered BN ring, which is a result of the σ-bonding interaction between two odd-electron B-B π-orbitals.
View Article and Find Full Text PDFStrained hydrocarbons constitute one of the most prominent classes of organic compounds. Among them, bicyclo[2.1.
View Article and Find Full Text PDFHumans and dogs are the two major hosts of Strongyloides stercoralis, an intestinal parasitic nematode. To better understand the phylogenetic relationships among S. stercoralis isolates infecting humans and dogs and to assess the zoonotic potential of this parasite, we analyzed mitochondrial Cox1, nuclear 18S rDNA, 28S rDNA, and a major sperm protein domain-containing protein genes.
View Article and Find Full Text PDFThe aim of the present study was to investigate the profile of surgical periodontal therapy performed at the Suidobashi Hospital of Tokyo Dental College, during the period of April 2010 through March 2011. A total of 112 periodontal surgeries in 69 patients (mean age: 51.4 years; 28 men and 41 women) were registered for the data analysis.
View Article and Find Full Text PDFThe aim of this retrospective clinical study was to evaluate 2-year follow-up results following regenerative periodontal surgery for intrabony defects using enamel matrix derivative (EMD). Thirteen patients (mean age: 53 years) with a clinical diagnosis of chronic periodontitis were subjected to data analysis. A total of 25 sites with intrabony defects received regenerative therapy with EMD.
View Article and Find Full Text PDFAim: To gain insight into the impact of periodontal surgery on oral health-related quality of life (QoL) of patients with periodontitis.
Material And Methods: Study participants were recruited from moderate to severe periodontitis patients. After initial periodontal therapy, participants received periodontal surgery.
Background: Cardiac troponin I (cTnI) is currently considered to be the most sensitive and specific biochemical marker of acute coronary syndrome and acute myocardial infarction. However, few reports have described the use of cTnI assays for evaluating abnormal hemodynamic load in children with congenital heart disease (CHD). It was hypothesized that significant hemodynamic overload due to a left-to-right shunt induces myocardial injury.
View Article and Find Full Text PDFThe aim of this retrospective clinical study was to evaluate the treatment of intrabony periodontal defects with enamel matrix derivative (EMD) during the early stages of healing. Sixteen patients aged 38-77 years with a clinical diagnosis of chronic periodontitis were subjected to data analysis. A total of 25 teeth with various osseous defects received regenerative therapy with EMD, and were followed for a minimum of 6 months.
View Article and Find Full Text PDFArtificial lungs have already been developed as complete artificial organs, and results of many investigations based on innovative concepts have been reported continuously. In open-heart surgery, artificial lungs are used for extracorporeal circulation to maintain gas exchange, and the commercial products currently available perform adequately, including providing for antithrombogenicity. However, patients after cardiopulmonary arrest or severe respiratory/circulatory failure have required long-term assist with extracorporeal membrane oxygenation (ECMO).
View Article and Find Full Text PDFPercutaneous cardiopulmonary support (PCPS) has been applied for cardiopulmonary arrest (CPA). We have developed a novel method of cardiopulmonary resuscitation using PCPS combined with liposome-encapsulated hemoglobin (TRM645) to improve oxygen delivery to vital organs. Ventricular fibrillation was electrically induced to an adult goat for 10 min.
View Article and Find Full Text PDFObjectives: This study was conducted to examine the relationship between provoked coronary spasm and clinical course in patients with acute myocardial infarction (AMI).
Background: Coronary spasm has a pathogenetic role in the occurrence of AMI and progressive atherosclerosis. There is no report that focused on the prognostic significance of provoked coronary spasm in AMI patients.
Objective: Significant Q-wave is sometimes invisible in the patients with triple vessel disease (TVD) even though TVD is a serious coronary heart disease. We offer the preliminary method to analyze the time-frequency profile of QRS in TVD patients.
Methods: Electrocardiograms (ECG) band-pass filtered through 50 to 300Hz were recorded from the persons without heart diseases (Normal group; n=24), the patients with single vessel disease (SVD group; n=12) and TVD (TVD group; n=12) and saved into PC.
We have been developing a pneumatic ventricular assist device (PVAD) system consisting of a diaphragm-type blood pump. The objective of the present study was to evaluate the flow pattern inside the PVAD, which may greatly affect thrombus formation, with respect to the inflow valve-mount orientation. To analyze the change of flow behavior caused by the orifice direction (OD) of the valve, the flow pattern in this pump was visualized.
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