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11.
Partially bio‐based tri‐ and hexaallyl monomers: Synthesis from naturally occurring myo‐inositol and polyaddition with dithiols 下载免费PDF全文
Atsushi Sudo Yugo Shirakawa Tomio Sakue 《Journal of polymer science. Part A, Polymer chemistry》2017,55(9):1524-1529
myo‐Inositol, a naturally occurring cyclic hexaol, was converted to 2,4,6‐tri‐O‐allyl‐myo‐inositol and 1,2,3,4,5,6‐hexa‐O‐allyl‐myo‐inositol. Polyaddition of the former product, a tri(allyl ether) bearing three hydroxyl groups, with dithiols yielded the corresponding networked polymers. Their glass transition temperatures (Tgs) were higher than those of networked polymers formed by the polyaddition of 1,3,5‐tri‐O‐methyl‐2,4,6‐tri‐O‐allyl‐myo‐inositol. This implied the reinforcement of the networks by hydrogen bonding between the hydroxyl groups. Polyaddition of the latter product, a hexa(allyl ether), with dithiols yielded the corresponding networked polymers with much higher Tgs than those of all of the aforementioned networked polymers. This implied that efficient use of the hexafunctional monomer leads to the formation of more densely crosslinked polymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1524–1529 相似文献
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T. Umecky T. Takamuku T. Aida T. Makino T. Aizawa M. Kanakubo 《Journal of solution chemistry》2014,43(9-10):1539-1549
2H and 17O NMR relaxation times, T 1(2H) and T 1(17O), and 2H NMR chemical shifts, δ(2H), in CO2-saturated CD3OD and C2D5OD solutions were measured at 313.2 K over the pressure range up to ~6 MPa. The rotational correlation times, τ r, of the CD and OD axes within CD3OD and C2D5OD molecules and the CO axis within the CO2 molecule were determined from T 1(2H) and T 1(17O), and the magnetic susceptibility-corrected chemical shifts, δ corr, were derived from δ(2H). The differences in τ r and δ corr observed between the two alcohol systems: τ r and δ corr of OD in C2D5OD, decreased rapidly with increasing CO2 concentration, while those of OD in CD3OD remained almost unchanged at mole fractions of CO2, \( x_{\text CO_{2}} \) , lower than ~0.25 and then slightly decreased at higher \( x_{\text CO_{2}} \) . The hydrogen bonding structure in C2D5OD was found to be gradually broken down by CO2 dissolution. On the other hand, in CD3OD, it has been revealed that the hydrogen bonding structure can persist at \( x_{\text CO_{2}} \) < ~0.25 but then collapses at higher \( x_{\text CO_{2}} \) . 相似文献
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Prof. Dr. Tsutomu Ishi-i Honoka Tanaka Rihoko Kichise Christopher Davin Takaaki Matsuda Dr. Naoya Aizawa Dr. In Seob Park Prof. Dr. Takuma Yasuda Taisuke Matsumoto 《化学:亚洲杂志》2021,16(15):2136-2145
The regulation of multicolor fluorescence changes in mechanochromic fluorescence (MCF) remains a challenging task. Herein, we report the regulation of MCF using a donor-acceptor structure. Two crystal polymorphs, BTD-pCHO(O) and BTD-pCHO(R) produced by the introduction of formyl groups to an MCF dye, respond to a mechanical stimulus, allowing a three-color fluorescence change. Specifically, the orange-colored fluorescence of the metastable BTD-pCHO(O) polymorph changed to a deep-red color in the amorphous-like state to finally give a red color in the stable BTD-pCHO(R) polymorph. This change occurred by mechanical grinding followed by vapor fuming. The two different crystal packing patterns were selectively regulated by the electronic effect of the introduced functional groups. The two types of selectively formed crystals in BTD(F)-pCHO bearing fluorine atoms, and BTD(OMe)-pCHO bearing methoxy groups, respond to mechanical grinding, allowing for the regulation of multicolor MCL from a three-color change to two different types of two-color changes. 相似文献
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Dr. Masayuki Iwasaki Miki Iyanaga Yuta Tsuchiya Yugo Nishimura Wenjuan Li Prof. Dr. Zhiping Li Prof. Dr. Yasushi Nishihara 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(9):2459-2462
A catalytic variant of the direct thiolation of arenes, bearing directing groups, with disulfides or thiols has been developed under palladium and copper co‐catalysis. Both sulfenyl moieties of the disulfide could be incorporated into the thiolated products, therefore, the reactions reached completion with only half an equivalent of disulfide, with respect to the starting arene. Experimental evidence suggested that the reaction proceeds through a PdII/PdIV mechanism. 相似文献
16.
Aizawa M Morikawa Y Namai Y Morikawa H Iwasawa Y 《The journal of physical chemistry. B》2005,109(40):18831-18838
The catalytic dehydration reaction processes of formic acid on a TiO2(110) surface at 350 K have been studied to visualize reaction intermediates and their dynamic behaviors by scanning tunneling microscopy. Three types of configurations of adsorbed formates on the surface were identified by their shapes and positions in STM images. Successive STM observations revealed transformations among the three configurations, i.e., bridge formate on a 5-fold coordinated Ti4+ row, bridge formate on an oxygen vacancy site with an oxygen atom of formate and on a 5-fold coordinated Ti4+ ion and with the other formate oxygen atom, and a monodentate formate on an oxygen vacancy site with an oxygen atom of formate. The decomposition of the monodentate formate to carbon monoxide and hydroxyl was also imaged, which is a rate-determining step in the catalytic dehydration of formic acid. Combined with first-principle DFT calculations, the overall reaction processes of the catalytic dehydration of formic acid on the surface have been elucidated. Oxygen vacancies on the surface that can be produced by dehydration of two hydroxyls in situ under the catalytic reaction conditions are essential for the reaction. 相似文献
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A new approach to transport improvement in a helical magnetic axis stellarator is proposed. First of all, the proposal is presented for the L = 1 system. The effective toroidal curvature term epsilon(T), defined as the sum of the usual toroidal curvature and one of the nearest satellite harmonics of the helical field, determines confinement conditions of localized trapped particles. There exists a certain correlation between the smallness of epsilon(T) and the omnigeneity. This approach would give rise to the possibility of a stellarator design study in a wider parameter domain than quasisymmetry approaches. 相似文献
19.
Bulk mechanical alloying (BMA) followed by hot pressing (HP) was used to prepare Mg2Si0.6Ge0.4 thermoelectric material with high densification. Starting from the elemental power mixture, the Mg2Si0.6Ge0.4 solid solution was solid‐state synthesized via BMA. In fact, the peaks for the cubic‐structured Mg2Si0.6Ge0.4 solid solution phase were detected after 300 cycles in BMA. The single phase of Mg2Si0.6Ge0.4 was synthesized at 600 cycles in BMA. Mg2Si0.6Ge0.4 showed p‐type semiconduction without doping. Effects of hot pressing conditions on thermoelectric properties were investigated. With increasing hot pressing temperature from 673 to 773 K and pressure from 500 MPa to 1 GPa, the electrical conductivity increased and the Seebeck coefficient decreased. The maximum figure of merit was obtained with the processing parameter of 600 cycles BMA and hot pressing at 773 K, 1 GPa for 1 h. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
20.