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X-ray photoelectron spectroscopy (XPS) is among the most utilized analytical methods for nitrogen-doped carbon materials. Clarifying the assignments of nitrogen-doped carbon materials with different degrees of carbonization, which relates to conjugated systems, is essential to correlate structures with the performance of various applications, but such precise assignments were challenging. In this work, precise analyses were conducted to overcome the difficulty to assign the peaks of carbon materials with different degrees of carbonization, different edges, and various nitrogen-containing functional groups in graphene nanoribbons (GNRs), such as nitrile, pyridinic, primary with/without charges, secondary with/without charge, tertiary without charges (graphitic nitrogen), and quaternary nitrogen. Electrons donated from hydrogen and Madelung potentials showed a higher correlation to the peak shift of C1s and N1s XPS spectra than Mulliken charges on nitrogen. Zigzag edges showed a greater influence on the peak shift of tertiary amine (graphitic nitrogen) than armchair edges on XPS spectra. Besides, as the degree of carbonization is increased from aromatic compound-like structures to GNRs, the peak positions of C–N in C1s and N1s XPS spectra shifted to higher binding energies. This research proved that XPS could be applied to the precise structural analyses of nitrogen-containing carbon materials.

Previous studies have shown that phosphorylation of the retinoid X receptor-α (RXRα) is associated with the development of hepatocellular carcinoma (HCC). However, these findings were revealed using HCC cell lines that express phosphorylated-RXRα (p-RXRα) proteins; therefore, it remains unclear whether p-RXRα affects hepatocarcinogenesis in vivo. Therefore, to investigate the biological function of p-RXRα in vivo, we developed a doxycycline-inducible ES cell line and transgenic mouse, both of which overexpress the phosphomimetic mutant form of RXRα, T82D/S260D, in a doxycycline-dependent manner. We found that the development of liver tumors, especially high-grade adenoma and HCC, was enhanced in diethylnitrosamine (DEN)-treated T82D/S260D-inducible mice. Moreover, the increased incidence of liver tumors in the transgenic mice was attributable to the promotion of cell cycle progression. Interestingly, the expression of β-catenin protein and its target gene cyclin D1 was elevated in the liver tumors of DEN-treated T82D/S260D-inducible mice, concurrent with increased cytoplasmic and nuclear β-catenin protein expression, indicating its stabilization and transcriptional activation. These results indicate that p-RXRα promotes DEN-induced hepatocarcinogenesis in mice through the activation of the β-catenin signaling pathway, suggesting that p-RXRα may serve as a possible therapeutic target for HCC.

A metal-free covalent triazine framework (CTF) was synthesized from 2,4,6-tricyano-1,3,5-triazine (TCT) through open-system and liquid-phase synthesis using trifluoromethanesulfonic acid as both a ...

Oxygen-containing carbon materials have been studied extensively because of their excellent dispersibility, absorptivity, separability, and supportability of catalysts. However, structural control by existing top-down methods is almost impossible. Our group has demonstrated that phloroglucinol (PG, 1,3,5-trihydroxybenzene) can be a promising raw material to synthesize structurally controlled oxygen-containing carbon materials. In this study, in addition to PG, hexahydroxybenzene (HHB), which has more oxygen and high symmetry, was used as the raw material, and a Lewis acid catalyst, tris (pentafluorophenyl) borane (TPB), was used to enhance the structural control rate and the removability of catalysts from the carbonized samples. The solubility of heat-treated HHB was lower than that of heat-treated PG, but the oxygen content of heat-treated HHB was higher than that of heat-treated PG even at 673 K. By adding TPB to PG, dibenzofuran-like structures formed, and the structural control rate increased up to 93.6%. Besides, the content of fluorine in the catalyst was reduced to 0%, indicating that TPB can be a promising recyclable catalyst to promote the structural control rate of carbonized PG.

X-ray photoelectron spectroscopy (XPS) is among the most powerful techniques to analyse structures of nitrogen-doped carbon materials. However, reported assignments of (1) graphitic nitrogen (N)/substitutional N, quaternary N (Q–N), or tertiary amine (T–N) and (2) pyrrolic N/secondary amine or T–N are questionable. Most reports assign peaks at ca. 401 eV as Q–N or graphitic N, whereas raw materials in most of those works contain neither counter anion nor halogen. Besides, the peak at ca. 400 eV has been assigned as pyrrolic N, but the presence of N–H is generally not confirmed. In this work, it was clarified that one of the reasons for the prevailing ambiguous assignments is the presence of N in heptagonal and pentagonal rings. The peaks at 400.1–401.2 eV were determined to be T–N, but not Q–N by analyzing graphitized polyimide (with the oxygen content of 0.01 at% or lower and the hydrogen content of 0 at%) using Raman spectroscopy, XPS, X-ray diffraction, total neutron scattering, elemental analysis, and molecular dynamics simulation. Besides, it was revealed that the peak at 400.1 eV originated from T–N on 5-membered rings or 7- and 5-membered rings, but not pyrrolic N because graphite including no hydrogen was used for analysis.

The vapor-phase dehydration of 1,3-butanediol (1,3-BDO) to produce 1,3-butadiene (BD) was investigated over yttrium zirconate, Y2Zr2O7, which was prepared through a hydrothermal aging process. 1,3-...

Carbonization process of pyromellitic dianhydride (PMDA)-4,4′-diaminodiphenyl ether (ODA)-type polyimide has been studied for decades. However, various reaction mechanisms have been proposed and the detailed mechanisms are still controversial. It is essential to understand the carbonized structures of PMDA-ODA-type polyimide before analyzing the defect structures in graphite. In this work, the carbonization mechanisms of polyimide heated at 1273 K or lower were unveiled and the methodology to analyze carbon materials containing nitrogen, oxygen, pentagons, and heptagons using computational spectral analysis combined with molecular dynamics simulation (ReaxFF) are exhibited. For example, the formations of isoimide and cyclic ether were estimated by ReaxFF, and the presence was supported by experimental and calculated X-ray photoelectron spectroscopy (XPS) and carbon-13 nuclear magnetic resonance (13C NMR) spectra of polyimide heated between 813 and 873 K. The formations of pentagons and heptagon, suggested by ReaxFF, were also supported by Raman and 13C NMR spectra of polyimide heated between 833 and 1273 K. This work also revealed that the previously reported structures were unstable and that amine in the basal plane was the most plausible structure in polyimide heated at 1073 K or higher, as clarified by XPS, ReaxFF, and the energy calculation.

The bromination reactivity of various types of polycyclic aromatic hydrocarbons (PAHs) with oxygen atoms and graphene with oxygen atoms was estimated by density functional theory calculation and experimentally clarified by analyzing bromination of PAHs using gas chromatography–mass spectrometry. In the experimental and theoretical bromination reactivity of PAHs, the presence of hydroxyl group increased the reactivity of PAHs because of electron-donating nature of the hydroxyl group but the other oxygen-containing functional groups such as lactone, ether, and ketone decreased the reactivity due to the electron-withdrawing nature of those groups. These effects of functional groups on the reactivity were also confirmed in graphene. The tendency of theoretical bromination reactivity of graphene was graphene with hydroxyl group > graphene with no group > graphene with lactone group > graphene with ether group > graphene with ketone group. Our study on the estimation of bromination reactivity of graphene edges provides the groundwork for the bromination of graphene edges.

Oxygen-containing carbon materials such as graphene oxide have been extensively studied because of their high dispersibility. However, the oxygen-containing functional groups in most carbon materials are not controlled. Uncontrollability of the synthesis is also one of factors that prevent industrialization. Carbon materials derived from phloroglucinol (PG), which show high solubility/dispersibility and controllability of functional groups, have been developed recently by our group. The high performance of carbonized PG originates from the thermally stable backbone structure of the benzene ring with hydroxy groups of PG. However, the degree of carbonization was low. In this study, five heteropoly acids (HPAs), which are thermally stable homogeneous strong acid catalysts, were used to promote carbonization of PG without losing the controllability of functional groups and the dispersibility. HPAs promoted etherification of hydroxy groups followed by C=C coupling reactions (furan cyclization) at 523 K. Furthermore, it was confirmed that particularly furan structures, which contribute to solubility/dispersibility in solvents, and thermal stability in air, could be maintained at 673 K as suggested by spectroscopies and thermogravimetric-differential thermal analysis. Among five HPAs, phosphotungstic acid worked as the excellent catalyst to promote carbonization of PG containing furan structures, exhibiting high solubility/dispersibility and high thermal stability in air.

Pentagons in carbon materials have attracted attentions because of the potential high chemical reactivity, band gap control, and electrochemical activity. However, it is challenging to prepare a carbon film with high pentagon density because of the curvature and the high reactivity caused by the presence of pentagons, and it is also challenging to estimate the percentage of pentagons in carbon materials because of the limitation of current analytical techniques. In this work, the percentage of pentagons in carbon materials was experimentally estimated for the first time using experimental and calculated C1s X-ray photoelectron spectroscopy and elemental analysis. Carbon films with 7% of pentagons (40% of pentagons compared to the raw material) with electrical resistivity of 1.1 × 104 Ω meter were prepared by heat treatment of corannulene at 873 K. On the other hand, fluoranthene and fullerene remained as non-film solid and powder without forming films at 873 K. Experimental and calculated Raman and IR spectra revealed the peaks of different types of pentagons. Decrement of pentagons in corannulene and fluoranthene heated at high temperatures can be explained mainly by the scission of C=C bond in pentagons, as suggested by the results of reactive molecular dynamics simulation (ReaxFF).

Introduction: Posterior circulation aneurysm constitutes 15%–20% of all intracerebral aneurysms. With the advancement of endovascular techniques, the microsurgery for posterior circulation aneurysms has been pushed back a little. Even the International Subarachnoid Aneurysmal Trial gave support to the concepts of endovascular procedures, but microsurgical modality should not be discouraged. We present our institutional experience of microsurgical techniques on posterior circulation aneurysms. Materials and Methods: We performed a retrospective analysis of 37 patients of posterior circulation aneurysm from 2015 to 2019, referred to Bantane Hospital, Japan. We included all posterior circulation aneurysms such as basilar tip, basilar trunk, and vertebral artery-posterior inferior cerebellar artery (VA-PICA) aneurysms, admitted and treated with clipping or bypass and trapping. We assessed the outcome as measured by modified Rankin Score (mRS), complications, and mortality. Results: Out of 37 patients, 10 cases were a basilar tip, one case was the basilar trunk, and 26 cases were VA-PICA aneurysm. Intraoperatively, neuromonitoring, indocyanine green dye, dual-image videoangiography (DIVA), and neuro endoscope were used. Two patients of basilar tip aneurysm developed third cranial nerve paresis and six patients of VA-PICA aneurysm developed lower cranial nerve paresis which resolved spontaneously. All the patients were discharged with mRS of 0 or 1. No mortality was recorded in our study. Conclusion: Microsurgical clipping of posterior circulation aneurysm is safe in unruptured aneurysm with a very low risk of mortality and morbidity under experienced hands. All postoperative complications in our study were transient and resolved with time with no residual deficits. Preoperative simulation, intraoperative neuromonitoring, DIVA, and neuro endoscope help achieve complete obliteration of aneurysmal sac and avoid complications.

Oxygen-containing carbon materials such as graphene oxide have been studied intensively for a decade because of the high oxygen content, which is beneficial to disperse carbon materials in solutions and to support either metals or metal oxides on carbon materials. However, various oxygen-containing functional groups exist on carbon materials and controlling the structures is almost impossible. In this work, phloroglucinol (PG), which has a symmetrical structure with three hydroxyl groups relative to six aromatic carbon atoms, was found to be the best precursor among PG, cyanuric acid, trimesic acid, and melamine because of the high yield (63 wt%) at 573 K even in an open system which is essential for mass production. The materials synthesized from PG also showed the high dispersibility and/or solubility in solvents (N-methyl-2-pyrrolidone and N,N-dimethylformamide) and the low temperature to form carbon materials (573 K), which can be explained from (002) and (10) in X-ray diffraction pattern. X-ray photoelectron spectroscopy, Fourier transform infrared spectrometer, carbon-13 nuclear magnetic resonance with the aid of calculation of both spectra and carbonization mechanisms revealed that the high solubility of carbonized PG originates from the presence of ether and cyclic ether, which were formed from dehydration of hydroxy groups, and also some remained hydroxyl groups in carbonized PG. Oxygen-containing groups in carbonized PG were effective as an antioxidant. In addition, the coating of carbonized PG on silica nanoparticles imparted conductivity and lubricity to silica nanoparticles.

Determination of the number of bromo groups and brominated positions of edges on carbon materials is essential for selective functionalization because the brominated positions influence their electronic structures. However, the determination is challenging because the analysis of introduced bromo groups on carbon materials is conventionally limited to quantitative analysis by X-ray photoelectron spectroscopy. In this work, infrared spectra (IR) of brominated aromatic compounds were analyzed experimentally and theoretically using reference aromatic compounds to verify that the calculated peak positions can be used to estimate the experimental peak positions of brominated aromatic compounds. IR spectra of brominated graphene nanoribbons (GNRs) with zigzag, armchair, and other edges were simulated as one of the carbon materials with clear edge structures. Their characteristic peak positions and tendencies of shifts were explained from the point of view of Mulliken charge, C–H and C=C length, and orbital hybridization. As the number of Br on GNRs increased, the peak positions basically shifted further, indicating that the density of Br and introduced positions of Br can be estimated from IR spectra. The detailed assignments obtained in this work will lead to selective functionalization of carbon materials.

Because perovskite crystals exhibit unique magnetic, conductive, and optical properties, they have been the subject of many fundamental investigations in various research fields. However, investigations related to their use as optoelectronic device materials are still in their early days. Regarding oxide perovskites, which have been investigated for a long time, the efficiency of photoluminescence (PL) induced by band-to-band transitions is extremely low because of the localized nature of the carriers in these materials. On the other hand, halide perovskites exhibit a highly efficient band-edge PL attributable to the recombination of delocalized photocarriers. Therefore, it is expected that this class of high-quality materials will be advantageous for optoelectronic devices such as solar cells and light-emitting diodes. In this Minireview, we discuss various aspects of the PL properties and carrier dynamics of SrTiO3 and CH3 NH3 PbX3 (X=I, Br), which are representative oxide and halide perovskites.

OBJECTIVES To determine the safety and efficacy of the combined regimen of paclitaxel and ifosfamide plus nedaplatin for patients with refractory or relapsed germ cell tumors and impaired renal function. METHODS Of a total of 68 patients who received paclitaxel, ifosfamide and nedaplatin chemotherapy for germ cell tumors, those with an estimated glomerular filtration rate

The primary objectives of the India National Gas Hydrate Program Expedition 02 (NGHP-02) were to obtain new data on the occurrence of gas hydrate systems and to advance the understanding of the controls on the formation of gas hydrate accumulations in the offshore of India. In accordance with the ultimate overall goal of the NGHP effort to assess the energy resource potential of marine gas hydrates in India, particular focus was placed on the exploration and evaluation of gas hydrate occurrences at high saturations in sand-rich systems. NGHP-02 operations were conducted from 3-March-2015 to 28-July-2015 off the eastern coast of India and included logging while drilling (LWD) operations at 25 locations, and coring and wireline logging operations at 10 locations, in the Krishna-Godavari and Mahanadi Basins. The formation of highly concentrated gas hydrate accumulations, which are more suitable for energy extraction, requires the presence of relatively coarse-grained sediments with porosity needed to support the migration and accumulation of gas, and the nucleation of gas hydrate. The results of downhole logging, coring and formation pressure testing operations during NGHP-02 have confirmed the presence of extensive sand-rich depositional systems throughout the deepwater portions of the Krishna-Godavari and Mahanadi Basins. Two areas of the Krishna-Godavari Basin, referred to as Areas B and C, contain substantial gas hydrate accumulations in sand-rich systems and therefore represent ideal candidate sites for future gas hydrate production testing. This summary and technical report includes a comprehensive synthesis of the geologic, geophysical, geochemical, and physical property data acquired during NGHP-02 as it relates to the controls on gas hydrate occurrence, particularly with regards to sand-hosted accumulations. In the Mahanadi Basin, despite the confirmation of extensive reservoir capacity, gas supply at the NGHP-02 sites was insufficient to charge the reservoirs with gas hydrates. In the Krishna-Godavari Basin, extensive reservoir systems were confirmed with sediment grain-sizes ranging from coarse-silts to gravels. These reservoirs range from fully- to partially-filled with gas hydrate. The gas is determined to be from only microbial sources, and in part migrated into the reservoirs from deeper systems. The controls on gas hydrate occurrence are complex and varied; and include substantial reservoir heterogeneity and sufficient permeability throughout the reservoirs and seals that allowed pervasive fluid flow into and through the hydrate-bearing systems. These discoveries are the most significant confirmation of the exploration approach that focuses on direct detection of hydrate reservoirs supported by comprehensive petroleum systems analyses.

Avoidance of complications during cerebral aneurysm surgery marks the future outcome in the patient. Various modalities such as adequate opening of the Sylvian fissure, motor-evoked potential, endoscope-assisted microsurgery, indocyanine green dye, and dual image video angiography are available to reduce these complications during surgery, either by prevention of injury to the small perforators or the parent artery. We present our experience at the Fujita Health University Banbuntane Hospital, Japan, of the cerebral aneurysm surgery along with the use of these modalities in our patients from September 2014 to December 2016 along with a brief review of the various techniques for avoidance of complications.

Vapor-phase catalytic dehydration of butanediols (BDOs) such as 1,3-, 1,4-, and 2,3-butanediol was investigated over yttria-stabilized tetragonal zirconia (YSZ) catalysts as well as monoclinic zirconia (MZ). BDOs were converted to unsaturated alcohols with some by-products over YSZ and MZ. YSZ is superior to MZ for these reactions in a view point of selective formation of unsaturated alcohols. Calcination temperature of YSZ significantly affected the products selectivity as well as the conversion of BDOs: high selectivity to unsaturated alcohols was obtained over the YSZ calcined at high temperatures over 800 °C. In the conversion of 1,4-butanediol at 325 °C, the highest 3-buten-1-ol selectivity of 75.3% was obtained over the YSZ calcined at 1050 °C, whereas 2,3-butanediol was less reactive than the other BDOs. In the dehydration of 1,3-butanediol at 325 °C, in particular, it was found that a YSZ catalyst with a Y2O3 content of 3.2 wt.% exhibited an excellent stable catalytic activity: the highest selectivity to unsaturated alcohols such as 2-buten-1-ol and 3-buten-2-ol over 98% was obtained at a conversion of 66%. Structures of active sites for the dehydration of 1,3-butanediol were discussed using a crystal model of tetragonal ZrO2 and a probable model structure of active site was proposed. The well-crystalized YSZ inevitably has oxygen defect sites on the most stable surface of tetragonal ZrO2 (101). The defect site, which exposes three cations such as Zr4+ and Y3+, is surrounded by six O2− anions. The selective dehydration of 1,3-butanediol to produce 3-buten-2-ol over the YSZ could be explained by tridentate interactions followed by sequential dehydration: the position-2 hydrogen is firstly abstracted by a basic O2− anion and then the position-1 hydroxyl group is subsequently or simultaneously abstracted by an acidic Y3+ cation. Another OH group at position 3 plays an important role of anchoring 1,3-butanediol to the catalyst surface. Thus, the selective dehydration of 1,3-butanediol could proceed via the speculative base-acid-concerted mechanism.

Vapor-phase isomerization of 3-pentenal to 2-pentenal was performed over various oxide catalysts. An amorphous SiO2 catalyst with a weak acidity and medium mesopore size showed a conversion over 82% with 2-pentenal selectivity higher than 95% at 250 °C. Several characterizations, such as thermogravimetric analysis, diffuse reflectance infrared Fourier-transform, temperature-programmed desorption of adsorbed NH3, and isotope experiment using deuterated SiO2, were performed to investigate the active sites on SiO2. A SiO2 with a specific pore size showed a stable catalytic activity after a rapid decrease at the initial stage of the reaction. The isomerization of 3-pentenal to 2-pentenal was found to be an equilibrium reaction: the pressure equilibrium constant was estimated to be ca. 5 at 250 °C. The weak acidic silanol groups on SiO2 were proved to be the active sites for the isomerization of 3-pentenal to 2-pentenal. A possible reaction mechanism was proposed: hydrogen of the silanol groups on SiO2 was coordinated to 2-pentenal with a form of six-membered ring, which can explain the primary product of cis isomer.

Epithelial–mesenchymal transition (EMT)—a fundamental process in embryogenesis and wound healing—promotes tumor metastasis and resistance to chemotherapy. While studies have identified signaling components and transcriptional factors responsible in the TGF-β-dependent EMT, whether and how intracellular metabolism is integrated with EMT remains to be fully elucidated. Here, we showed that TGF-β induces reprogramming of intracellular amino acid metabolism, which is necessary to promote EMT in non-small cell lung cancer cells. Combined metabolome and transcriptome analysis identified prolyl 4-hydroxylase α3 (P4HA3), an enzyme implicated in cancer metabolism, to be upregulated during TGF-β stimulation. Further, knockdown of P4HA3 diminished TGF-β-dependent changes in amino acids, EMT, and tumor metastasis. Conversely, manipulation of extracellular amino acids induced EMT-like responses without TGF-β stimulation. These results suggest a previously unappreciated requirement for the reprogramming of amino acid metabolism via P4HA3 for TGF-β-dependent EMT and implicate a P4HA3 inhibitor as a potential therapeutic agent for cancer., Through metabolome and transcriptome analyses, Nakasuka et al find that TGF-β-induced epithelial–mesenchymal transition (EMT) in non-small cell lung cancer cells is associated with reprogramming of amino acid metabolism. They also identify P4HA3 as a key enzyme involved in these changes altogether providing insights into potential mechanisms of metastasis.

The objective of this study was to compare the efficacy of abiraterone acetate with that of bicalutamide in combination with gonadotropin-releasing hormone (GnRH) antagonist treatment for patients with high-risk metastatic hormone-sensitive prostate cancer (mHSPC). A total of 149 patients with mHSPC who underwent treatment at our hospital and affiliated hospitals between December 2013 and July 2020 were retrospectively identified. Fifty patients were administered abiraterone acetate (1000 mg/day) plus prednisolone (5 mg/day) with a GnRH antagonist (degarelix) (group A), and 99 patients were administered bicalutamide (80 mg/day) with a GnRH antagonist (group B). The prostate-specific antigen (PSA) progression-free survival (PSA-PFS) was significantly longer in group A than in group B. Abiraterone acetate therapy and Gleason score were significant independent factors of PSA-PFS. Using propensity score matching, 56 matched patients were obtained. The PSA-PFS (p

Deep, hot, and more alive than we thought Marine sediments represent a massive microbial ecosystem, but we still do not fully understand what factors shape and limit life underneath the seafloor. Analyzing samples from a subduction zone off the coast of Japan, Heuer et al. found that microbial life, in particular bacterial vegetative cells, decreases as depth and temperature increases down to ∼600 meters below the seafloor, corresponding to temperatures of ∼70°C. Below this limit, endospores are common—a remnant, and a potential reservoir, of bacterial life. Deeper still is a sterile zone, and below 1000 meters is a scalding realm populated by vegetative cells. At such great depths, high concentrations of acetate and sulfate coexist, and there are also signs of hyperthermophilic methanogenesis. These data provide a fascinating window into an extreme and inhospitable environment that nonetheless supports microbial life. Science , this issue p. 1230

The aim of this work is to develop an effective catalyst for the conversion of butanediols, which is derivable from biomass, to valuable chemicals such as unsaturated alcohols. The dehydration of 1,4-, 1,3-, and 2,3-butanediol to form unsaturated alcohols such as 3-buten-1-ol, 2-buten-1-ol, and 3-buten-2-ol was studied in a vapor-phase flow reactor over sixteen rare earth zirconate catalysts at 325 &deg, C. Rare earth zirconates with high crystallinity and high specific surface area were prepared in a hydrothermal treatment of co-precipitated hydroxide. Zirconates with heavy rare earth metals, especially Y2Zr2O7 with an oxygen-defected fluorite structure, showed high catalytic performance of selective dehydration of 1,4-butanediol to 3-buten-1-ol and also of 1,3-butanediol to form 3-buten-2-ol and 2-buten-1-ol, while the zirconate catalysts were less active in the dehydration of 2,3-butanediol. The calcination of Y2Zr2O7 significantly affected the catalytic activity of the dehydration of 1,4-butanediol: a calcination temperature of Y2Zr2O7 at 900 &deg, C or higher was efficient for selective formation of unsaturated alcohols. Y2Zr2O7 with high crystallinity exhibits the highest productivity of 3-buten-1-ol from 1,4-butanediol at 325 &deg, C.

Isotropic pitch-based carbon fiber has been utilized for various applications such as thermal insulation materials for high-temperature furnace and additives for slide member, but the structure of the carbon fiber is still under debate. This is because the precursor pitch contains various aromatic compounds in addition to the complicated oxidation and carbonization reaction during production process of carbon fiber. In this work, oxidation processes of model compounds of pitch such as pyrene (sp2C H with zigzag-like edges), triphenylene (sp2C H with armchair edges), fluorene (pentagon with sp3CH2), and 9-methylanthracene (hexagon with sp3CH3) were analyzed using mass spectrometry, elemental analysis, infrared (IR), Raman, and X-ray photoelectron spectroscopy (XPS) in addition to calculation such as molecular dynamic simulation with a reactive force field (ReaxFF) and simulation of IR, Raman, and XPS spectra (Gaussian09). Combination of calculations and experiments revealed that oxidation proceeded in the order of zigzag-like edges > sp3CH3 > sp2CH2 > armchair edges, and the quinone formed by oxidation worked as a precursor for a crosslinking reaction. It is expected that the results of this work, which revealed the origin of the crosslinking, could lead to improve properties as well as to estimate the detailed structures of isotropic pitch-based carbon fiber.

Vapor-phase aldol condensation of butanal to form 2-ethyl-2-hexenal was carried out over several oxide catalysts such as SiO2-Al2O3, Al2O3, ZrO2, and SiO2. Catalysts with moderate and strong acid sites such as Al2O3 and SiO2-Al2O3 were active for the reaction in the initial period, whereas they deactivated rapidly. In contrast, SiO2 with weak acidity showed a low but a stable catalytic activity for the formation of 2-ethyl-2-hexenal. Thermogravimetric analyses of the samples used after the reactions indicate that SiO2 has the smallest amount of carbonaceous species that contributed to its stable activity among the tested catalysts. SiO2 catalysts with different pore sizes and specific surface areas were examined: SiO2 with a mean pore diameter of 10 nm and a surface area of 295 m2 g−1 showed the best catalytic performance and gave a 2-ethyl-2-hexenal selectivity of 90% at a conversion of 48% at 240 °C. In the catalytic test using deuterated SiO2, which was prepared by contacting SiO2 with deuterated water before the reaction, it was confirmed by a mass spectrometer that the deuterium atom of SiOD was transferred to a 2-ethyl-2-hexenal molecule during the reaction. It is indicated that silanol groups on the SiO2 surface played a role as an active site.

Carbon materials such as graphene and graphene nanoribbon with zigzag and armchair edges have attracted much attention because of various applications such as electronics, batteries, adsorbents, and catalyst supports. Preparation of carbon materials with different edge structures at a large scale is essential for the future of carbon materials, but it is generally difficult and expensive because of the necessity of organic synthesis on metal substrates. This work demonstrated a simple preparation method of carbon materials with zigzag and armchair edges with/without nonmetallic silica supports from aromatic compounds such as tetracene with zigzag edges and chrysene with armchair edges and also determined the edge structures in detail by three types of analyses such as (1) reactive molecular dynamic simulation with a reactive force field, (2) Raman and infrared (IR) spectra combined with calculation of spectra, and (3) reactivity analyzed by oxidative gasification using thermogravimetric analysis. Two different types of carbon materials with characteristic Raman and IR spectra could be prepared. These carbon materials with different edge structures also clearly showed different tendency in oxidative gasification. This work did not only show the simple preparation method of carbon materials with different edge structures, but also contributes to the development of detailed analyses for carbon materials.

CO2 removal and sensing, especially by amine groups, are necessary to prevent global warming. However, understanding the dynamic mechanism of CO2 capture on nitrogen sites remains challenging. We f...

Cu-Ni/SiO2 catalyst was developed by impregnation assisted with citric acid for the vapor-phase hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL). The prepared catalysts were characterized by using X-ray powder diffraction (XRD), transmission electron microscope (TEM), temperature-programed reduction, thermogravimetry analysis, and X-ray fluorescence analysis. The XRD analysis and the TEM observation of the catalyst samples indicate that the usage of citric acid in the preparation process of impregnation improved the dispersion of Cu and Ni metal on SiO2. A Cu-Ni/SiO2 catalyst with Cu loading of 4 wt.% and Ni of 16 wt.% showed the best performance in the hydrogenation of LA to GVL under ambient H2 pressure at a high weight hourly space velocity (WHSV) of 13.2 h−1 and 250 °C: the conversion was 98.2% and the GVL selectivity was 97.6%. The catalyst prepared by citric acid-assisted impregnation showed the resistance to catalyst deactivation.

Vapor-phase dehydration of 1,4-butanediol and 3-buten-1-ol to produce 1,3-butadiene was investigated over rare earth oxides such as Lu2O3, Yb2O3, Tm2O3, Er2O3, and Sc1.0Yb1.0O3. In the dehydration of 3-buten-1-ol, heavy rare earth oxides such as Lu2O3, Yb2O3, and Er2O3 showed high catalytic performance for the selective formation of 1,3-butadiene with producing small amount of propylene whereas acidic catalysts such as alumina decomposed 3-buten-1-ol into propylene. In particular, over Yb2O3 calcined at 800 °C, 3-buten-1-ol was converted with a yield of 1,3-butadiene higher than 95% at 340 °C. In the dehydration of 1,4-butanediol, furthermore, we developed an efficient catalytic system: 1,3-butadiene was produced via an intermediate, 3-buten-1-ol, over Yb2O3 with an excellent yield of 96% at 360 °C and a high contact time of 2.26 h. Yb2O3 successfully inhibited the major side reaction such as decomposition of 3-buten-1-ol to propylene and provided the selective production of 1,3-butadiene from 1,4-butanediol.

Vapor phase dehydration of 5-amino-1-pentanol to produce piperidine was investigated over various oxide catalysts such as ZrO2, TiO2, Al2O3 and SiO2. Among the tested catalysts, SiO2 selectively produced piperidine at 300 °C. A high 5-amino-1-pentanol conversion of 99.9% with a piperidine selectivity of 94.8% was achieved over weak acidic SiO2. In an experiment using isotope such as deuterated water, surface hydroxy groups of SiO2 are concluded to be the active centers.

Introduction: Basilar aneurysms represent 5%–7% of all intracranial aneurysms. The main goal of open surgery is to achieve complete obliteration of the aneurysmal sac using minimal invasive technique while emphasizing on avoidance of complication. Materials and Methods: We performed a retrospective cohort study of nine cases of unruptured basilar tip aneurysm referred to the Fujita Health University Banbuntane-Hotokukai Hospital, Japan. The objective of the study was to analyze the surgical outcomes of unruptured basilar tip aneurysm. Results: Nine patients with unruptured basilar tip aneurysm were referred to our hospital between 2015 and 2017. The median size of the aneurysm and age were 4.00 mm (interquartile range [IQR] = 3.25–6.75 mm) and 58 years (IQR = 54–70 years), respectively. Five patients (55.6%) were presented with multiple intracranial aneurysms. Surgical adjuncts such as intraoperative neuromonitoring, intraoperative indocyanine green (ICG) angiography with dual-image videoangiography (DIVA), and neuroendoscope were used. Two patients developed transient postoperative oculomotor nerve palsy which resolved spontaneously. The median duration of surgery and days of hospitalization were 292 min (IQR = 237.5–350.5 min) and 12 days (IQR = 12–25 days), respectively. There was no mortality recorded in this case series. Conclusion: Microsurgical clipping of basilar tip aneurysm is safe in unruptured basilar tip aneurysm with a low risk of postoperative mortality or morbidity. All complications reported in this case series were transient with no long-term sequalae. The improved safety profile of microsurgical technique is due to the availability of intraoperative neuromonitoring, neuroendoscope, ICG, and DIVA. The application of multimodality technique in neurovascular surgery has also helped to achieve complication avoidance. The obliteration of the aneurysmal sac helps to restore the laminar blood flow in the bifurcation and distal blood vessels and improves the brain perfusion.

Vapor-phase catalytic dehydration of 2,3-butanediol (2,3-BDO) to form 1,3-butadiene (BD) via 3-buten-2-ol (3B2OL) was studied over various single metal oxide catalysts. Among the catalysts, Sc2O3 prepared under hydrothermal (HT) conditions at 200 °C followed by 800 °C calcination showed the most excellent catalytic activity. The crystallization of precursor ScOOH during HT aging noticeably enhances the catalytic activity of the resulting Sc2O3 for the formation of 3B2OL in the dehydration of 2,3-BDO. The formation rate of 3B2OL from 2,3-BDO over the HT-aged Sc2O3 was twice as high as Sc2O3 without HT aging. Calcination temperatures of Sc2O3 are also important: calcination at 800 °C is efficient for the selective formation of 3B2OL from 2,3-BDO. The HT-aged Sc2O3 also showed an excellent catalytic activity for the formation of BD with the yield higher than 80% in the dehydration of 2,3-BDO at 411 °C.

Long-term stability of catalysts is one of important factors in heterogeneous catalysis. Solid acid catalysts are widely used in various reactions in the chemical industry, whereas they readily deactivate in most cases because of coke deposition on the acid sites. Therefore, efficient methods for controlling deactivation of solid acid catalysts are highly required. A method including both the doping of transition metals and the reaction operation in H2 flow (named as Metal-H2 method) is effective for suppressing coke deposition on solid acids in various cases. Although the Metal-H2 methodology has been utilized in some processes by different research groups, it has not been systematically summarized. In this review, we originally define the Metal-H2 method, and summarize the specific applications of the Metal-H2 method for controlling deactivation in cracking, reforming, dehydration, aldol condensation, and other processes.

Vapor-phase catalytic dehydration of 1,4-butanediol (1,4-BDO) was investigated over Y2O3-ZrO2 catalysts. In the dehydration, 1,3-butadiene (BD) together with 3-buten-1-ol (3B1OL), tetrahydrofuran, and propylene was produced depending on the reaction conditions. In the dehydration over Y2O3-ZrO2 catalysts with different Y contents at 325°C, Y2Zr2O7 with an equimolar ratio of Y/Zr showed high selectivity to 3B1OL, an intermediate to BD. In the dehydration at 360°C, a BD yield higher than 90% was achieved over the Y2Zr2O7 calcined at 700°C throughout 10 h. In the dehydration of 3B1OL over Y2Zr2O7, however, the catalytic activity affected by the calcination temperature is roughly proportional to the specific surface area of the sample. The highest activity of Y2Zr2O7 calcined at 700 °C for the BD formation from 1,4-BDO is explained by the trade-off relation in the activities for the first-step dehydration of 1,4-BDO to 3B1OL and for the second-step dehydration of 3B1OL to BD. The higher reactivity of 3B1OL than saturated alcohols such as 1-butanol and 2-butanol suggests that the C=C double bond of 3B1OL induces an attractive interaction to anchor the catalyst surface and promotes the dehydration. A probable mechanism for the one-step dehydration of 1,4-BDO to BD was discussed.

Objective and Background: To evaluate possible roles for indocyanine green (ICG)-based FLOW 800 software in surgical treatment of cerebral arteriovenous malformations (AVMs). Methods: We perform ICG videoangiography several times for each step of AVM resection to elucidate feeders, drainers, and cerebral perfusion. Results: Since 2010, 22 AVM surgeries in our department have been conducted using FLOW 800 intraoperatively. We demonstrated ICG angiograms, color-coded images, and semi-quantitative curves for AVMs. By reviewing all these modalities, we would define vascular structure of the AVM, proceed with resection, and finally recheck for any remnant. Conclusions: ICG FLOW 800 software helps the surgeon to recognize feeding and draining vessels of an AVM intraoperatively. Further studies to evaluate semi-quantitative acquired data regarding blood flow and tissue perfusion are warranted.

We studied the optical responses of organic–inorganic halide perovskite CH3NH3PbBr3 single crystals doped with heterovalent Bi3+ ions (electron densities up to 2.3 × 1012 cm–3). The Bi doping causes no significant changes in the band gap energy but leads to an enhanced Urbach tail and photoluminescence blue shift. On the basis of the time-resolved photoluminescence measurements, we attribute the PL response to a shorter carrier lifetime induced by Bi doping, which results in a reduced photon recycling effect (i.e., the repeated emission and reabsorption of photons inside the crystal). We discuss the physical relation between Bi concentration and the optical and electric properties of Bi-doped CH3NH3PbBr3 and reveal the unique nature of the Bi3+ ion as a dopant in halide perovskites.

Organic-inorganic hybrid lead halide perovskites are currently a most attractive class of materials since they have emerged as a solar cell material that realizes both high efficiency and simple low-cost fabrication. The power conversion efficiencies of perovskite solar cells now exceed 22%, which is comparable to that of commercially available CIGS and CdTe thin film solar cells. The key to further improvement is understanding the physical origin of the high efficiency of the perovskite solar cells, and a tremendous effort to come closer to this target has been made through numerous experiments. In this review article, we discuss the optoelectronic properties of perovskite CH3NH3PbX3 (X = I and Br) solar cell materials. Special attention is given to the free carrier recombination and photon recycling (the re-absorption of photons emitted by radiative recombination of photocarriers) processes in CH3NH3PbX3 single crystals, because a deep understanding of these processes is crucial for improving the solar ...

Edges of carbon materials have been known to work as active sites for various applications such as catalysts, adsorbent, and electrodes, but selecting precursors for carbon materials with controlled edges in the absence of metallic substrate is challenging. This work developed a method to select the superior precursors instantaneously using molecular dynamic simulation. This simulation predicted that hydrogen in precursors gasified and the hydrogen attacked the active sites in precursors upon carbonization, causing the decrement of active sites. Thus, it is essential to reduce the concentration of hydrogen in precursors and it is also necessary to introduce reactive functional groups near the active site to protect the active sites. We indeed synthesized the selected precursors such as diethynyl anthracene, diethynyl chrysene, divinyl naphthyridine, and divinyl phenanthroline and proved that edges in those precursors were maintained even after carbonization at 773 K using diffuse reflectance infrared Fourier transform and X-ray photoelectron spectroscopy with the aid of spectra simulated by density functional theory calculation. Especially, ca. 100% of edge structures of zigzag edges and armchair edges in diethynyl anthracene and diethynyl chrysene was maintained even after carbonization at 773 K.

Vapor-phase catalytic dehydration of 1,5-pentanediol (1,5-PDO) was investigated over monoclinic ZrO2 catalysts modified with basic oxides. An unsaturated alcohol, 4-penten-1-ol (4P1OL), was produced together with the formation of tetrahydropyran, δ-valerolactone, 1,4-pentadiene, pentanal, 1-pentanol, and 5-hydroxypentanal, etc. Among the modified ZrO2 catalysts, only ZrO2 modified with MgO enhanced the selectivity to 4P1OL efficiently. The most active modified catalyst was found to have 20 mol% MgO and a calcination at 800 °C (MgO/ZrO2), and the selectivity of 4P1OL exceeded 83% at 400 °C. A pulse adsorption measurement of several chemicals clarified adsorptive interaction between a reactant and a catalyst at 220 °C: the interaction between 1,5-PDO and MgO/ZrO2 was stronger than the other adsorbates and catalysts. Another strong adsorptive interaction between 1,4-butanediol and CaO/ZrO2, which was effective in the dehydration of 1,4-butanediol to produce 3-buten-1-ol, was also observed.

Vapor-phase hydrogenation of levulinic acid (LA) and methyl levulinate (ML) to γ-valerolactone (GVL) was performed over non-noble metal-based catalysts such as Cu/Al2O3, Ni/SiO2 and Co/SiO2. The catalytic activity and stability of the Cu-, Ni- and Co-based catalysts for the formation of GVL from ML and LA were investigated and compared at a low contact time of 0.3 h. In the hydrogenation of ML to GVL, the order of the catalytic activity for the conversion of ML was Cu/Al2O3 > Co/SiO2 > Ni/SiO2. Cu/Al2O3 was the most selective for the formation of GVL, whereas it was unstable in contrast to the other catalysts. In the hydrogenation of LA to GVL, the order of the catalytic activity for the conversion of LA was Ni/SiO2 > Cu/Al2O3 > Co/SiO2, which is the same as the order of the catalyst stability, while Cu/Al2O3 was the most selective for the formation of GVL from LA. The reactions were also performed in N2 atmosphere in order to study the reaction pathways. Methyl 4-hydroxypentanoate was supposed to be the intermediate in the hydrogenation of ML to GVL, whereas the reaction pathways in the hydrogenation of LA to GVL were dependent on the catalyst species. Based on the TG analysis of the used catalysts, it was found that LA led to more severe catalyst deactivation than ML did.

Vapor-phase catalytic production of 2,3-butanediol from acetoin and diacetyl was investigated over the supported metal catalysts such as Ni, Co, Cu, and Ag. A yield of 2,3-butanediol higher than 90% can be obtained from both acetoin and diacetyl over Ni/SiO 2 catalyst in an H 2 flow at 150 °C. Since the hydrogenation is an exothermic reaction, a low temperature is favorable to gain a full production of 2,3-butanediol. It was found that the equilibrium among 2,3-butanediol, acetoin, and diacetyl could be achieved at a contact time of the reactants with catalyst longer than 1.67 h. The pressure equilibrium constants in the hydrogenation were calculated by the outlet gas composition.

Fibrodysplasia ossificans progressiva (FOP) is a rare and intractable disease characterized by extraskeletal bone formation through endochondral ossification. Patients with FOP harbor point mutations in ACVR1, a type I receptor for BMPs. Although mutated ACVR1 (FOP-ACVR1) has been shown to render hyperactivity in BMP signaling, we and others have uncovered a mechanism by which FOP-ACVR1 mistransduces BMP signaling in response to Activin-A, a molecule that normally transduces TGF-β signaling. Although Activin-A evokes enhanced chondrogenesis in vitro and heterotopic ossification (HO) in vivo, the underlying mechanisms have yet to be revealed. To this end, we developed a high-throughput screening (HTS) system using FOP patient–derived induced pluripotent stem cells (FOP-iPSCs) to identify pivotal pathways in enhanced chondrogenesis that are initiated by Activin-A. In a screen of 6, 809 small-molecule compounds, we identified mTOR signaling as a critical pathway for the aberrant chondrogenesis of mesenchymal stromal cells derived from FOP-iPSCs (FOP-iMSCs). Two different HO mouse models, an FOP model mouse expressing FOP-ACVR1 and an FOP-iPSC–based HO model mouse, revealed critical roles for mTOR signaling in vivo. Moreover, we identified ENPP2, an enzyme that generates lysophosphatidic acid, as a linker of FOP-ACVR1 and mTOR signaling in chondrogenesis. These results uncovered the crucial role of the Activin-A/FOP-ACVR1/ENPP2/mTOR axis in FOP pathogenesis., FOPにおける骨化を抑える方法の発見 --FOPの異所性骨形成のシグナル伝達メカニズムの解明--. 京都大学プレスリリース. 2017-08-01.

Hydrogenation of γ-valerolactone to 1,4-pentanediol was performed over both precious and base metal catalysts in a continuous flow reactor under H 2 pressure. Cu/ZnO catalyst showed the highest catalytic performance for the formation of 1,4-pentanediol from γ-valerolactone. Low reaction temperatures such as 140 °C were preferable for achieving 1,4-pentanediol, and high temperatures led to the further conversion of 1,4-pentanediol to 2-methyltetrahydrofuran and 1-pentanol. High H 2 pressures and moderate H 2 flow rates such as 90 cm 3 min −1 were effective for the formation of 1,4-pentanediol. Calcination temperature of Cu/ZnO significantly affected its catalytic activity. A Cu/ZnO catalyst with a Cu metal loading of 40 wt.% gave the γ-valerolactone conversion of 82.3% with the 1,4-pentanediol selectivity of 99.2% at 140 °C under 1.5 MPa of H 2 pressure, while no decrease in the catalytic activity was observed for 10 h.

Despite recent advances in the carbonization of organic crystalline solids like metal-organic frameworks or supramolecular frameworks, it has been challenging to convert crystalline organic solids into ordered carbonaceous frameworks. Herein, we report a route to attaining such ordered frameworks via the carbonization of an organic crystal of a Ni-containing cyclic porphyrin dimer (Ni2-CPDPy). This dimer comprises two Ni–porphyrins linked by two butadiyne (diacetylene) moieties through phenyl groups. The Ni2-CPDPy crystal is thermally converted into a crystalline covalent-organic framework at 581 K and is further converted into ordered carbonaceous frameworks equipped with electrical conductivity by subsequent carbonization at 873–1073 K. In addition, the porphyrin’s Ni–N4 unit is also well retained and embedded in the final framework. The resulting ordered carbonaceous frameworks exhibit an intermediate structure, between organic-based frameworks and carbon materials, with advantageous electrocatalysis. This principle enables the chemical molecular-level structural design of three-dimensional carbonaceous frameworks., Carbon-based materials are promising alternatives to noble metal catalysts, but their structures are typically disordered and difficult to control. Here, the authors obtain ordered carbonaceous frameworks with advantageous electrocatalytic properties via the carbonization of nickel-containing porphyrin dimer networks.

Vapor-phase catalytic dehydration of 1,4-butanediol (1,4-BDO) was investigated over modified ZrO 2 catalysts. In the dehydration of 1,4-BDO over monoclinic ZrO 2 (m-ZrO 2 ), an unsaturated alcohol, 3-buten-1-ol (3B1OL), was produced together with tetrahydrofuranand γ-butyrolactone. Among alkaline earth metal oxide modifiers, CaO with an appropriate content significantly enhanced the 3B1OL selectivity of m-ZrO 2 . The modification of CaO was more efficient over m-ZrO 2 than tetragonal ZrO 2 . CO 2 -TPD measurements reveal that CaO supported on m-ZrO 2 calcined at 800 °C or higher generated new basic sites, which are attributed from Ca-O-Zr hetero-linkages, for the effective formation of 3B1OL from 1,4-BDO. In order to create more Ca-O-Zr hetero-linkages on the m-ZrO 2 surface efficiently, additional ZrO 2 was loaded on m-ZrO 2 together with CaO via a co-impregnation method. At an appropriate weight ratio of CaO/ZrO 2 = 7/2 loaded on m-ZrO 2 , both the 1,4-BDO conversion and the 3B1OL selectivity were enhanced greatly. Especially, the 3B1OL selectivity exceeded 90% at 350 °C.