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1.
Synthesis of thermally stable aromatic poly(spiroorthocarbonate)s having a Cardo or bent structure 下载免费PDF全文
Masaki Moritsugu Ryota Seto Kozo Matsumoto Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2016,54(10):1409-1416
Novel poly(spiroorthocarbonate)s [poly(SOC)]s having a Cardo or bent structure were synthesized by polycondensation of several bis‐catechols having fluorene (BCFL), spirobisindane (BCSPI), or spirobischromane (BCSPC) in the structure with 2,2,6,6‐tetrachlorobenzo[1,2‐d:4,5‐d’]bis[1,3]dioxole (4ClBD). Synthesis of poly(SOC)s was confirmed by NMR and IR spectrometry. The poly(SOC)s obtained from BCFL or BCSPC were soluble in common organic solvents. The glass transition temperature of the poly(SOC)s was not detected by differential scanning calorimetry (DSC) in the range of 50–300 °C. The 10 wt % decomposition temperature of the poly(SOC)s was found to be above 400 °C. These results indicated the high thermal stability of the poly(SOC)s. Soluble poly(SOC)s could be possessed to form a film on a glass plate by the spin coat method. The obtained polymer films were 0.2 μm in thickness with 95% light transmission in the optical wavelength range. These results suggested that the Cardo or bent structure may block the packing of the main‐chain of the structure, which improves the solubility of the polymers, increases transparency, and enhances the thermal stability of SOCs. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1409‐1416 相似文献
2.
In‐Depth Understanding of the Chemical Properties of Rarely Explored Carbide Cluster Metallofullerenes: A Case Study of Sc2C2@C3v(8)‐C82 that Reveals a General Rule 下载免费PDF全文
Wenting Cai Muqing Chen Lipiao Bao Dr. Yunpeng Xie Prof. Dr. Takeshi Akasaka Prof. Dr. Xing Lu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(8):3449-3454
The chemical properties of carbide‐cluster metallofullerenes (CCMFs) remain largely unexplored, although several new members of CCMFs have been discovered recently. Herein, we report the reaction between Sc2C2@C3v(8)‐C82, which is viewed as a prototypical CCMF because of its high abundance, and 3‐triphenylmethyl‐5‐oxazolidinone ( 1 ) to afford the corresponding pyrrolidino derivative Sc2C2@C3v(8)‐C82(CH2)2NTrt ( 2 ; Trt=triphenylmethyl). Single‐crystal X‐ray crystallography studies of 2 revealed that the reaction takes place at a [6,6]‐bond junction, which is directly over the encapsulated C2 unit and is far from either of the two scandium atoms. On the basis of theoretical calculations and by considering previously reports, we have found that a hexagonal carbon ring on the cage of Sc2C2@C3v(8)‐C82 is highly reactive toward different reagents due to the overlap of high p‐orbital axis vector (POAV) angles and large LUMO coefficients. We propose that this highly concentrated area of reactivity is generated by the encapsulation of the Sc2C2 cluster because this region is absent from the empty fullerene C3v(8)‐C82. Moreover, the absorption and electrochemical results confirm that derivative 2 is more stable than pristine Sc2C2@C3v(8)‐C82, thus illuminating its potential applications. 相似文献
3.
Prof. Kengo Hanaya Kaho Yamoto Prof. Kazuaki Taguchi Prof. Kazuaki Matsumoto Prof. Shuhei Higashibayashi Prof. Takeshi Sugai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(47):e202201677
The chemical modification of proteins is an effective technique for manipulating the properties and functions of proteins, and for creating protein-based materials. The N-terminus is a promising target for single-site modification that provides modified proteins with uniform structures and properties. In this paper, a copper(II)-mediated aldol reaction with 2-pyridinecarboxaldehyde (2-PC) derivatives is proposed as an operationally simple method to selectively modify the N-terminus of peptides and proteins at room temperature and physiological pH. The copper(II) ion activates the N-terminal amino acids by complexation with an imine of the N-terminal amino acid and 2-PCs, realizing the selective formation of the nucleophilic intermediate at the N-terminus. This results in a stable carbon-carbon bond between the 2-PCs and the α-carbon of various N-terminal amino acids. The reaction is applied to four different proteins, including biopharmaceuticals such as filgrastim and trastuzumab. The modified trastuzumab retains the human epidermal growth factor receptor 2 recognition activity. 相似文献
4.
Kawamorita Soichiro Ahadito Bijak Riyandi Naota Takeshi 《Transition Metal Chemistry》2020,45(3):173-186
Transition Metal Chemistry - The synthesis, structure and photophysical properties of dinuclear bis(phenylpyridine)(salicylaldiminato)Ir(III) complexes bearing polymethylene linkers are described... 相似文献
5.
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
6.
Takashi Machida Dr. Takeshi Iwasa Prof. Dr. Tetsuya Taketsugu Prof. Dr. Kazuki Sada Dr. Kenta Kokado 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(36):8028-8034
Aggregation-induced emission (AIE) is a fascinating phenomenon because of the applications of luminescent materials in the aggregated state, which exploit the large structural changes of the molecules in the excited state. Recently, it was reported that triphenylphosphane derivatives show AIE behavior in which they undergo potentially large structural changes in the excited state. Inspired by this report, photoinduced pyramidal inversion behavior of phosphanes was investigated. In photochemical experiments, the prepared P-stereogenic phosphanes exhibited photoracemization in dilute solution, and a negative correlation was observed between the photoracemization and the AIE phenomenon. Theoretical computations revealed that the inversion barrier in the excited state was much smaller than that in the ground state. This is the first report on the photoinduced pyramidal inversion behavior of phosphanes, which will provide new and unexplored applications. 相似文献
7.
Dr. Takeshi Matsumoto Risa Yamamoto Dr. Masanori Wakizaka Dr. Akinobu Nakada Prof. Dr. Ho-Chol Chang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(43):9609-9619
The global demand for energy and the concerns over climate issues renders the development of alternative renewable energy sources such as hydrogen (H2) important. A high-spin (hs) FeII complex with o-phenylenediamine (opda) ligands, [FeII(opda)3]2+ (hs- [6R] 2+), was reported showing photochemical H2 evolution. In addition, a low-spin (ls) [FeII(bqdi)3]2+ (bqdi: o-benzoquinodiimine) (ls- [0R] 2+) formation by O2 oxidation of hs- [6R] 2+, accompanied by ligand-based six-proton and six-electron transfer, revealed the potential of the complex with redox-active ligands as a novel multiple-proton and -electron storage material, albeit that the mechanism has not yet been understood. This paper reports that the oxidized ls- [0R] [PF6]2 can be reduced by hydrazine giving ls-[FeII(opda)(bqdi)2][PF6]2 (ls- [2R] [PF6]2) and ls-[FeII(opda)2(bqdi)][PF6]2 (ls- [4R] [PF6]2) with localized ligand-based proton-coupled mixed-valence (LPMV) states. The first isolation and characterization of the key intermediates with LPMV states offer unprecedented molecular insights into the design of photoresponsive molecule-based hydrogen-storage materials. 相似文献
8.
9.
Masato Kawamoto Yasuyuki Mori Akihiko Tsuge Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2022,60(8):1416-1421
Anionic ring-opening polymerization (ROP) behavior of trans-cyclohexene carbonate (CHC) using metal alkoxides as initiators was investigated. As a result, lithium tert-butoxide-initiated ROP of CHC with a high-monomer concentration (10 M) at low temperature (−15 to −10°C) proceeded to afford a poly(trans-cyclohexene carbonate) (PCHC) without undesired side reactions such as mainly backbiting. The suppression of side reactions enables the control of the molecular weight (Mn = 2400–6100) of PCHC with low molar-mass dispersity values (Mw/Mn = 1.16–1.22). Furthermore, by increasing the feed ratio of the monomer to the initiator, the molecular weight increases proportionally, indicating a controllable polymerization. The results of a matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis, a kinetic study, and a chain extension experiment suggested a living nature of this ROP using lithium tert-butoxide. 相似文献
10.
Ion gels are an emerging class of polymer gels in which a three-dimensional polymer network swells with an ionic liquid. Ion gels have drawn considerable attention in various fields such as energy and biotechnology owing to their excellent properties including nonvolatility, nonflammability, high ionic conductivity, and high thermal and electrochemical stability. Since the first report on ion gels (published ∼30 years ago), diverse functional ion gels exhibiting impressive physicochemical properties have been reported. In this review, recent developments in functional ion gels that can modulate their physical properties in response to environmental conditions are outlined. Stimuli-responsive ion gels that can adaptively undergo phase transitions in response to thermal and light stimuli are initially discussed, followed by an evaluation of diverse self-healing ion gels that can spontaneously mend mechanical damage through judiciously designed ion-gel networks. 相似文献