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排序方式: 共有1713条查询结果,搜索用时 218 毫秒
1.
Guangtao Duan Takuya Matsunaga Akifumi Yamaji Seiichi Koshizuka Mikio Sakai 《国际流体数值方法杂志》2021,93(1):148-175
Corrective matrix that is derived to restore consistency of discretization schemes can significantly enhance accuracy for the inside particles in the Moving Particle Semi‐implicit method. In this situation, the error due to free surface and wall boundaries becomes dominant. Based on the recent study on Neumann boundary condition (Matsunaga et al, CMAME, 2020), the corrective matrix schemes in MPS are generalized to straightforwardly and accurately impose Neumann boundary condition. However, the new schemes can still easily trigger instability at free surface because of the biased error caused by the incomplete/biased neighbor support. Therefore, the existing stable schemes based on virtual particles and conservative gradient models are applied to free surface and nearby particles to produce a stable transitional layer at free surface. The new corrective matrix schemes are only applied to the particles under the stable transitional layer for improving the wall boundary conditions. Three numerical examples of free surface flows demonstrate that the proposed method can help to reduce the pressure/velocity fluctuations and hence enhance accuracy further. 相似文献
2.
Chiral cyclic [n]spirobifluorenylenes consisting of helically arranged quaterphenyl rods, illustrating partial units of woven patterns, were designed and synthesized as a new family of carbon nanorings. The synthesis was accomplished by the Ni(0)-mediated Yamamoto-coupling of chiral spirobifluorene building blocks. The structures of the cyclic 3-, 4-, and 5-mers were determined by X-ray crystallographic analysis. These carbon nanorings exhibited a strong violet colored emission with high quantum yields in solution (95%, 93%, and 94% for 3-, 4-, and 5-mer, respectively). Other spectroscopic properties, including their chiroptical properties, were also investigated. The g-values for circularly polarized luminescence were found to be in the order of 10−3. Characteristic spiroconjugation induced by multiple (≧3) bifluorenyl units, for example the even-odd effect of the number of units in the matching of the signs of the orbitals, was also indicated by DFT calculations.Chiral cyclic [n]spirobifluorenylenes consisting of helically arranged quaterphenyl rods, illustrating partial units of woven patterns, were designed and synthesized as a new family of carbon nanorings. 相似文献
3.
Dr. Chaolu Eerdun Thi Hien Thuy Nguyen Takuya Okayama Satoshi Hisanaga Prof. Dr. Jun-ichiro Setsune 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(22):5777-5786
The hexapyrrole-α,ω-dicarbaldehydes 1 a and 1 b were metallated with CuII, NiII, and PdII to give bimetallic complexes where a pair of 3 N+O four-coordinate metal planes are helically distorted and the central 2,2′-bipyrrole subunit adopts a cis or trans conformation. X-ray crystallographic analysis of the bisCu complex revealed a closed form with a cis-2,2′-bipyrrole subunit and an open form with a trans-2,2′-bipyrrole subunit. The bisPd complexes took a closed form both in the solid state and in solution. They are regarded as single helicates of two turns and the energy barrier for the interchange between an M helix and a P helix was remarkably influenced by the bulky 3,3′-substituent of the central 2,2′-bipyrrole subunit. Although the bisNi complexes adopt a closed form in the solid state, they exist as a homohelical open C2-symmetric form or a heterohelical open Ci-symmetric form in solution. A theoretical study suggested that the closed form of 1 a Pd was stabilized by the Pd–Pd interaction. Compound 1 a Pd was reversibly oxidized by one electron at 0.14 V versus ferrocene/ferrocenium (Fc/Fc+) and this oxidized species showed Vis/NIR absorption bands at λ=767 and 1408 nm. 相似文献
4.
5.
Prof. Dr. Tomoaki Tanase Dr. Kanako Nakamae Yume Okawa Mami Hamada Dr. Arimasa Matsumoto Prof. Dr. Takayuki Nakajima Prof. Dr. Takuya Nakashima Prof. Dr. Tsuyoshi Kawai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(8):e202104060
A P-stereogenic linear tetraphosphine tetraoxide, (R,R)- or (S,S)-dpmppm(=O)4, was synthesized to prepare C2 dinuclear M(hfa)3 complexes (M=Eu, Tb, Y) as the first example of lanthanide(III) complexes with P-chiral multidentate phosphine oxides. The mononuclear M(hfa)3 complexes (M=Eu, Y) with a P-chiral diphosphine dioxide, tpdpb(=O)2, were also prepared, and comparison of their photophysical properties for the EuIII complexes revealed that significant chiral induction from the P-chiral centers arises on the achiral M(hfa)3 units through intramolecular π-π stacking constraint in the dinuclear system. 相似文献
6.
Rei Tomifuji Prof. Takuya Kurahashi Prof. Seijiro Matsubara 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(38):8987-8991
The development and use of a multiple-activation catalyst with ion-paired Lewis acid and Brønsted acid in an asymmetric aza-Diels–Alder reaction of simple dienes (non-Danishefsky-type electron-rich dienes) was achieved by utilizing the [FeBr2]+[FeBr4]− combination prepared in situ from FeBr3 and chiral phosphoric acid. Synergistic effects of the highly active ion-paired Lewis acid [FeBr2]+[FeBr4]− and a chiral Brønsted acid are important for promoting the reaction with high turnover frequency and high enantioselectivity. The multiple-activation catalyst system was confirmed using synchrotron-based X-ray absorption fine structure measurements, and theoretical studies. This study reveals that the developed catalyst promoted the reaction not only by the interaction offered by the ion-paired Lewis acid and the Brønsted acid but also noncovalent interactions. 相似文献
7.
Dr. Kenta Arai Takahiko Matsunaga Haruhito Ueno Nozomi Akahoshi Yuumi Sato Dr. Gaurango Chakrabarty Prof. Dr. Govindasamy Mugesh Prof. Dr. Michio Iwaoka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(55):12751-12760
At the redox-active center of thioredoxin reductase (TrxR), a selenenyl sulfide (Se−S) bond is formed between Cys497 and Sec498, which is activated into the thiolselenolate state ([SH,Se−]) by reacting with a nearby dithiol motif ([SHCys59,SHCys64]) present in the other subunit. This process is achieved through two reversible steps: an attack of a cysteinyl thiol of Cys59 at the Se atom of the Se−S bond and a subsequent attack of a remaining thiol at the S atom of the generated mixed Se−S intermediate. However, it is not clear how the kinetically unfavorable second step progresses smoothly in the catalytic cycle. A model study that used synthetic selenenyl sulfides, which mimic the active site structure of human TrxR comprising Cys497, Sec498, and His472, suggested that His472 can play a key role by forming a hydrogen bond with the Se atom of the mixed Se−S intermediate to facilitate the second step. In addition, the selenenyl sulfides exhibited a defensive ability against H2O2-induced oxidative stress in cultured cells, which suggests the possibility for medicinal applications to control the redox balance in cells. 相似文献
8.
Motoko S. Asano Sho Hashimoto Takuya Shinozuka Yasutaka Fushimi 《Molecular physics》2019,117(19):2664-2672
ABSTRACTInteraction between a zinc porphyrin (ZnPor) as the end-group and poly(9,9-di-n-octylfluorene-2,7-vinylene) (PFV) as the main chain in a porphyrin end-modified fluorescent conjugated polymer, ZnPFV, was studied by time-resolved electron paramagnetic resonance (EPR) and fluorescence spectroscopy. While fluorescence from the PFV part of ZnPFV showed a spectral profile almost identical to that of a PFV oligomer without end-modification, the emission spectrum of the ZnPor part exhibited a much broader profile compared to that of the reference zinc porphyrin monomer. Based on the analysis of lifetimes and quantum yields, it was found that radiative rate constant of the ZnPor part was enhanced by nearly three times. The observed unusual enhancement in the radiative rate constant was rationalised in terms of a partial π-conjugation between the end group and the main chain, as a result of co-planarisation in fluid solution. On the other hand, the time-resolved EPR spectrum of ZnPFV at 100?K basically showed a similar spectral pattern to that of the reference zinc porphyrin, but with significant differences in zero-field spitting parameters and initial population ratios. The π-system of the excited triplet state is deduced to deviate from D4h symmetry in the end zinc porphyrin groups. The obtained results show that interaction of the porphyrin end group with the main chain of the polymer significantly influences the excited singlet state properties of the porphyrin, while its triplet state properties were affected to a lesser extent. 相似文献
9.
Joy Ann Panis Prof. Marine Louis Arnaud Brosseau Shouhei Katao Florencio de los Reyes Prof. Takuya Nakashima Dr. Rémi Métivier Dr. Clémence Allain Prof. Tsuyoshi Kawai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(44):e202201012
We synthesized two bichromophoric difluoroboron-β-diketonates (DFB) connected in para and meta positions by using cyclohexane diamine as a chiral bridge ( para and meta (R/S)-CyDFB ). TD-DFT calculations revealed that the variation in connectivity of the DFB units leads to different spatial arrangements and a chirality inversion of the bichromophoric DFB. Higher gabs values were obtained in (R/S)-CyDFB connected in para as compared to meta position. Aggregation of para (R/S)-CyDFB in mixture of solvents increase the glum values as compared to its monomeric form. Ultrasonication and heating induced the formation of highly ordered nano-helical wires of para (R/S)-CyDFB that increased the glum values to 0.015. On the other hand, meta (R/S)-CyDFB failed to form highly ordered self-assembled wires due to hindered H-binding sites. These observations indicate that the chiroptical properties of DFB bi-chromophore system can be modulated with self-assembly and spatial arrangement of the chromophores. 相似文献
10.
Mostafa Abdelrahman Sho Hirata Takuya Mukae Tomohiro Yamada Yuji Sawada Magdi El-Syaed Yutaka Yamada Muneo Sato Masami Yokota Hirai Masayoshi Shigyo 《Molecules (Basel, Switzerland)》2021,26(5)
Garlic (Allium sativum) is the second most important Allium crop that has been used as a vegetable and condiment from ancient times due to its characteristic flavor and taste. Although garlic is a sterile plant that reproduces vegetatively through cloves, garlic shows high biodiversity, as well as phenotypic plasticity and environmental adaptation capacity. To determine the possible mechanism underlying this phenomenon and to provide new genetic materials for the development of a novel garlic cultivar with useful agronomic traits, the metabolic profiles in the leaf tissue of 30 garlic accessions collected from different geographical regions, with a special focus on the Asian region, were investigated using LC/MS. In addition, the total saponin and fructan contents in the roots and cloves of the investigated garlic accessions were also evaluated. Total saponin and fructan contents did not separate the garlic accessions based on their geographical origin, implying that saponin and fructan contents were clone-specific and agroclimatic changes have affected the quantitative and qualitative levels of saponins in garlic over a long history of cultivation. Principal component analysis (PCA) and dendrogram clustering of the LC/MS-based metabolite profiling showed two major clusters. Specifically, many Japanese and Central Asia accessions were grouped in cluster I and showed high accumulations of flavonol glucosides, alliin, and methiin. On the other hand, garlic accessions grouped in cluster II exhibited a high accumulation of anthocyanin glucosides and amino acids. Although most of the accessions were not separated based on country of origin, the Central Asia accessions were clustered in one group, implying that these accessions exhibited distinct metabolic profiles. The present study provides useful information that can be used for germplasm selection and the development of new garlic varieties with beneficial biotic and abiotic stress-adaptive traits. 相似文献