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Noboru Sato Yuichi Funato Yasuyuki Fukushima Takeshi Momose Mitsuo Koshi Yukihiro Shimogaki 《国际化学动力学杂志》2020,52(6):359-367
We established a gas-phase, elementary reaction model for chemical vapor deposition of silicon carbide from methyltrichlorosilane (MTS) and H2, based on the model developed at Iowa State University (ISU). The ISU model did not reproduce our experimental results, decomposition behavior of MTS in the gas phase in an environment with H2. Therefore, we made several modifications to the ISU model. Of the reactions included in existing models, 236 were lacking in the ISU model, and thus were added to the model. In addition, we modified the rate constants of the unimolecular reactions and the recombination reactions, which were treated as a high-pressure limit in the ISU model, into pressure-dependent rate expressions based on the previous reports (to yield the ISU+ model), for example, H2(+M) → H + H(+M), but decomposition behavior remained poorly reproducible. To incorporate the pressure dependencies of unimolecular decomposition rate constants, and to increase the accuracies of these constants, we recalculated the rate constants of five unimolecular decomposition reactions of MTS using the Rice-Ramsperger-Kassel-Marcus method at the CBS-QB3 level. These chemistries were added to the ISU+ model to yield the UT2014 model. The UT2014 model reproduced overall MTS decomposition. From the results of our model, we confirmed that MTS mainly decomposes into CH3 and SiCl3 at the temperature around 1000°C as reported in the several studies. 相似文献
3.
This paper is our attempt, on the basis of physical theory, to bring more clarification on the question “What is life?” formulated in the well-known book of Schrödinger in 1944. According to Schrödinger, the main distinguishing feature of a biosystem’s functioning is the ability to preserve its order structure or, in mathematical terms, to prevent increasing of entropy. However, Schrödinger’s analysis shows that the classical theory is not able to adequately describe the order-stability in a biosystem. Schrödinger also appealed to the ambiguous notion of negative entropy. We apply quantum theory. As is well-known, behaviour of the quantum von Neumann entropy crucially differs from behaviour of classical entropy. We consider a complex biosystem S composed of many subsystems, say proteins, cells, or neural networks in the brain, that is, We study the following problem: whether the compound system S can maintain “global order” in the situation of an increase of local disorder and if S can preserve the low entropy while other increase their entropies (may be essentially). We show that the entropy of a system as a whole can be constant, while the entropies of its parts rising. For classical systems, this is impossible, because the entropy of S cannot be less than the entropy of its subsystem . And if a subsystems’s entropy increases, then a system’s entropy should also increase, by at least the same amount. However, within the quantum information theory, the answer is positive. The significant role is played by the entanglement of a subsystems’ states. In the absence of entanglement, the increasing of local disorder implies an increasing disorder in the compound system S (as in the classical regime). In this note, we proceed within a quantum-like approach to mathematical modeling of information processing by biosystems—respecting the quantum laws need not be based on genuine quantum physical processes in biosystems. Recently, such modeling found numerous applications in molecular biology, genetics, evolution theory, cognition, psychology and decision making. The quantum-like model of order stability can be applied not only in biology, but also in social science and artificial intelligence. 相似文献
4.
Formulation of Aluminum Chloride Phthalocyanine in Pluronic™ P‐123 and F‐127 Block Copolymer Micelles: Photophysical properties and Photodynamic Inactivation of Microorganisms 下载免费PDF全文
Bruno Henrique Vilsinski Adriana Passarella Gerola Junior Adalberto Enumo Katieli da Silva Souza Campanholi Paulo Cesar de Souza Pereira Gustavo Braga Noboru Hioka Elza Kimura André Luiz Tessaro Wilker Caetano 《Photochemistry and photobiology》2015,91(3):518-525
Aluminum Chloride Phthalocyanine (AlPcCl) can be used as a photosensitizer (PS) for Photodynamic Inactivation of Microorganisms (PDI). The AlPcCl showed favorable characteristics for PDI due to high quantum yield of singlet oxygen (ΦΔ) and photostability. Physicochemical properties and photodynamic inactivation of AlPcCl incorporated in polymeric micelles of tri‐block copolymer (P‐123 and F‐127) against microorganisms Staphylococcus aureus, Escherichia coli and Candida albicans were investigated in this work. Previously, it was observed that the AlPcCl undergoes self‐aggregation in F‐127, while in P‐123 the PS is in a monomeric form suitable for PDI. Due to the self‐aggregation of AlPcCl in F‐127, this formulation did not show any effect on these microorganisms. On the other hand, AlPcCl formulated in P‐123 was effective against S. aureus and C. albicans and the death of microorganisms was dependent on the PS concentration and illumination time. Additionally, it was found that the values of PS concentration and illumination time to eradicate 90% of the initial population of microorganisms (IC90 and D90, respectively) were small for the AlPcCl in P‐123, showing the effectiveness of this formulation for PDI. 相似文献
5.
Eriko Sato Noboru Tamari Hideo Horibe 《Journal of polymer science. Part A, Polymer chemistry》2019,57(24):2474-2480
Graft copolymers show microphase separated structure as seen in block copolymers and have lower intrinsic viscosity than block copolymers because of a branching structure. Therefore, considering molding processability, especially for polymers containing rigid segments, graft copolymers are useful architectures. In this work, graft copolymers containing rigid poly(diisopropyl fumarate) (PDiPF) branches were synthesized by full free‐radical polymerization process. First, synthesis of PDiPF macromonomers by addition‐fragmentation chain transfer (AFCT) was investigated. 2,2‐Dimethyl‐4‐methylene‐pentanedioic acid dimethyl ester was found to be an efficient AFCT agent for diisopropyl fumarate (DiPF) polymerization because of the suppression of undesired primary radical termination, which significantly took place when common AFCT agent, methyl 2‐(bromomethyl)acrylate, was used. Copolymerization of PDiPF macromonomer with ethyl acrylate accomplished the generation of the graft copolymer having flexible poly(ethyl acrylate) backbone and rigid PDiPF branches. The graft copolymer showed a microphase separated structure, high transparency, and characteristic thermal properties to PDiPF and poly(ethyl acrylate). © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2474–2480 相似文献
6.
trans-Stilbene, 1, 1-diphenylethylene, and α-methylstyrene were allowed to react with dibenzylmagnesium to form their oligomers in hexamethylphosphortriamide (HMPA). One and two molecules of stilbene and 1, 1-diphenylethylene were incorporated into the magnesium carbon bond, and the carbanions obtained in HMPA were stable in analogy with the anionic living polymer having alkali cation as the gegenion in eithers. Intense coloration was observed during the reaction between α-methylstyrene and dibenzylmagnesium as well as in the case of stilbene and 1, 1-diphenylethylene. The low molecular weight products which were formed after a long time in the reaction between α-methylstyrene and dibenzylmagnesium were found to have no magnesium-carbon bond. It was considered that the cleavage of the propagating chain occurred gradually after the rapid propagation had proceeded to consume the monomer. 相似文献
7.
Synthesis,Characterization, and Electronic Structures of Porphyrins Fused with Polycyclic Aromatic Ring Systems 下载免费PDF全文
Prof. Dr. Tetsuo Okujima Dr. John Mack Dr. Jun Nakamura Gugu Kubheka Prof. Dr. Tebello Nyokong Dr. Hua Zhu Naoki Komobuchi Prof. Dr. Noboru Ono Prof. Dr. Hiroko Yamada Prof. Dr. Hidemitsu Uno Prof. Dr. Nagao Kobayashi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(41):14730-14738
A series of porphyrins fused with acenaphthylene, phenanthroline, and benzofluoranthene polycyclic aromatic rings were prepared by means of a 3+1 porphyrin synthesis approach and subsequent retro‐Diels–Alder reaction of bicyclo[2.2.2]octadiene‐fused precursors. Analysis of the magnetic circular dichroism spectra and the results of time‐dependent DFT calculations are used to identify the reasons for the trends observed in the wavelengths and relative intensities of the Q bands of the products. Michl's perimeter model is used as a conceptual framework to explain the changes in the relative energies of the frontier π‐molecular orbitals. 相似文献
8.
Fujiko Iwasaki Hideyuki Nishiyama Noriko Manabe Masanori Yasui Noboru Matsumura 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):429-430
Abstract Novel metal-carbene complexes (4) with a metallapentalene framework have been obtained from hypervalent diazadiselenathiapentalenes (3) by treating with Pt(PPh3)4, Pd(PPh3)4 and RhCl(PPh3)3. X-Ray investigations revealed that the central hypervalent sulfur atom in 3 was substituted by a metal atom to form M-Se bonds in the resultant metallapentalene framework. 相似文献
9.
10.
André Luiz Tessaro Vagner Roberto Batistela Augusto César Gracetto Hueder Paulo Moisés de Oliveira Rosana Lazara Sernaglia Vagner Roberto de Souza Wilker Caetano Noboru Hioka 《Journal of Physical Organic Chemistry》2011,24(2):155-161
Benzoporphyrin monoacid derivatives, here named B3A and B3B, are promising new drugs for photodynamic therapy. Although both isomers show interesting characteristics as photosensitizing compounds, they have some distinct physicochemical properties such as the tendency to self‐aggregate in water‐rich media. Because pH drives the presence of each species, the pKa of these compounds assumes strategic importance. However, traditional micro‐titration methods and UV–Vis absorption techniques fail to give reliable pKa values due to the characteristics of this highly complex system, such as the precipitation of hydrophobic species, close pKa values, and high absorption band superposition. In the present work, chemometric tools are employed to evaluate pKa, and the kinetic tendency of monomers to undergo self‐aggregation is investigated. In solvent mixtures at low water percentage in ethanol, both B3A and B3B are stabilized in a monomeric state. However, in mixtures with a high water content, self‐aggregation takes place, mainly under a mild pH acid condition (3 < pH < 6), in which the prevalent protolytic species of both isomers is the neutral charged form, compounds with carboxylic and porphyrin free‐base groups. It is demonstrated that both isomers can undergo aggregation following a self‐catalytic mechanism, which is 2000 times slower to B3A than B3B. For B3A, the aggregation is manifested by a decrease in the monomer band with the aggregation band probably superposed to that of the monomer. For B3B, together with the decrease in the monomer band, a new band related to self‐aggregates is observed. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献