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排序方式: 共有56条查询结果,搜索用时 15 毫秒
1.
Koji Ishizu Satoru Minematsu Takashi Fukutomi 《Journal of polymer science. Part A, Polymer chemistry》1990,28(5):1091-1099
We have studied the structural changes on poly(2-hydroxyethyl methacrylate) (PHEMA)/polystyrene (PS) blends by means of phase growth of microheterophase pattern on a template surface composed of poly[2-hydroxyethyl methacrylate (HEMA)-g-styrene (S)] graft copolymer (lamellar shape). The PS macromonomer was synthesized by free radical polymerization of S monomer initiated by a functional initiator [2,2'-azobis(2-(2-imidazolin-2-yl)propane: VA-061] in the presence of a degradative chain transfer agent, followed by an end-capping reaction with p-chloromethylstyrene (CMS). Poly(HEMA-g-S) graft copolymers were prepared by free radical copolymerization of these vinylbenzyl-terminated PS macromonomers with HEMA comonomer. 相似文献
2.
The anisotropy factor g, one of the optical properties of biological tissues, has a strong influence on the calculation of the scattering coefficient μ s in inverse Monte Carlo (iMC) simulations. It has been reported that g has the wavelength and absorption dependence; however, few attempts have been made to calculate μ s using g values by taking the wavelength and absorption dependence into account. In this study, the angular distributions of scattered light for biological tissue phantoms containing hemoglobin as a light absorber were measured by a goniometric optical setup at strongly (405 nm) and weakly (664 nm) absorbing wavelengths to obtain g. Subsequently, the optical properties were calculated with the measured values of g by integrating sphere measurements and an iMC simulation, and compared with the results obtained with a conventional g value of 0.9. The μ s values with measured g were overestimated at the strongly absorbing wavelength, but underestimated at the weakly absorbing wavelength if 0.9 was used in the iMC simulation. 相似文献
3.
Self‐Replication and Amplification of Enantiomeric Excess of Chiral Multifunctionalized Large Molecules by Asymmetric Autocatalysis
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Prof. Dr. Tsuneomi Kawasaki Mai Nakaoda Yutaro Takahashi Yusuke Kanto Nanako Kuruhara Kenji Hosoi Prof. Dr. Itaru Sato Arimasa Matsumoto Prof. Dr. Kenso Soai 《Angewandte Chemie (International ed. in English)》2014,53(42):11199-11202
Self‐replication of large chiral molecular architectures is one of the great challenges and interests in synthetic, systems, and prebiotic chemistry. Described herein is a new chemical system in which large chiral multifunctionalized molecules possess asymmetric autocatalytic self‐replicating and self‐improving abilities, that is, improvement of their enantioenrichment in addition to the diastereomeric ratio. The large chiral multifunctionalized molecules catalyze the production of themselves with the same structure, including the chirality of newly formed asymmetric carbon atoms, in the reaction of the corresponding achiral aldehydes and reagent. The chirality of the large multifunctionalized molecules controlled the enantioselectivity of the reaction in a highly selective manner to construct multiple asymmetric stereogenic centers in a single reaction. 相似文献
4.
Junko Fukutomi Yuko Adachi Akari Kaneko Atsuomi Kimura Hideaki Fujiwara 《Journal of inclusion phenomena and macrocyclic chemistry》2007,58(1-2):115-122
The inclusion complex formation of 4-sulfothiacalix[4]arene sodium salt (STCAS) and Xe has been investigated by using hyperpolarized
129Xe NMR spectroscopy. Our new continuous-flow type hyperpolarizing system has advantageous capabilities that can supply hyperpolarized
gases continuously and directly to a sample solution in a NMR tube. Consequently saturated Xe concentration in the aqueous
solution of STCAS is maintained during the NMR experiment, and 129Xe NMR spectra can be obtained in remarkably short time. STCAS concentration dependence of 129Xe chemical shift has been analyzed in an elaborated way by a computer method as well as a simple graphic method that we have
proposed. The association constant K:13.6±0.8 M−1 at 25 °C was obtained, and further analysis of the temperature dependence has successfully given thermodynamic parameters
of enthalpy (ΔH) and entropy (ΔS) for the inclusion complex formation: ΔH = −11.9±1.9 kJ mol−1 and ΔS = −17.4±5.8 JK−1 mol−1. The energetic aspects of complex formation are discussed from the size effect and from the molecular theory of standard
entropy, and a release of definite number of water molecules from STCAS cavity is suggested in the inclusion complex formation
with Xe. 相似文献
5.
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7.
Mitsutoshi Fukuda Makoto Fukutomi Yoshio Kato Tsutomu Hashimoto 《Journal of Polymer Science.Polymer Physics》1974,12(5):871-890
A series of polystyrenes with weight-average molecular weight M?w up to 1.3 × 107 was prepared by anionic polymerization in tetrahydrofuran (THF). Each sample was characterized by gel-permeation chromatography, light scattering, and viscometry. It was found that each sample had an almost symmetrical and very narrow molecular weight distribution (M?w/M?n < 1.07). The mean-square unperturbed radius of gyration 〈S2〉0 was determined in trans-decalin at 20.4°C as 〈S2〉0 = 7.86 × 10?18M?w (cm2). The particle scattering factor was well represented by the Debye equation irrespective of solvent in the range of M?w < 4 × 106, and only a small deviation was observed in benzene at higher molecular weights. The penetration function Ψ ≡ A2M2/4π3/2NA〈S〉23/2 was found to approach a relatively low asymptotic value of 0.21–0.23 at molecular weights above 2 × 106 in benzene at 30°C, where A2 is the second virial coefficient and NA is Avogrado's number. It was also found that the theta temperature in trans-decalin was affected by the nature of polymer samples. A difference of about 3°C in the theta temperature was observed between two series of anionic polystyrenes, one prepared in THF and the other in benzene, but there was practically no difference in unperturbed chain dimension. 相似文献
8.
Dr. Zachary T. Gossage Nanako Ito Prof. Tomooki Hosaka Prof. Ryoichi Tatara Prof. Shinichi Komaba 《Angewandte Chemie (International ed. in English)》2023,62(43):e202307446
The solid-electrolyte interphase (SEI) is key to stable, high voltage lithium-ion batteries (LIBs) as a protective barrier that prevents electrolyte decomposition. The SEI is thought to play a similar role in highly concentrated water-in-salt electrolytes (WISEs) for emerging aqueous batteries, but its properties remain unknown. In this work, we utilized advanced scanning electrochemical microscopy (SECM) and operando electrochemical mass spectrometry (OEMS) techniques to gain deeper insight into the SEI that occurs within highly concentrated WISEs. As a model, we focus on a 55 mol/kg K(FSA)0.6(OTf)0.4 electrolyte and a 3,4,9,10-perylenetetracarboxylic diimide negative electrode. For the first time, our work showed distinctly passivating structures with slow apparent electron transfer rates alike to the SEI found in LIBs. In situ analyses indicated stable passivating structures when PTCDI was stepped to low potentials (≈−1.3 V vs. Ag/AgCl). However, the observed SEI was discontinuous at the surface and H2 evolution occurred as the electrode reached more extreme potentials. OEMS measurements further confirmed a shift in the evolution of detectable H2 from −0.9 V to <−1.4 V vs. Ag/AgCl when changing from dilute to concentrated electrolytes. In all, our work shows a combined approach of traditional battery measurements with in situ analyses for improving characterization of other unknown SEI structures. 相似文献
9.
Aoki S Sakurama K Matsuo N Yamada Y Takasawa R Tanuma S Shiro M Takeda K Kimura E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(35):9066-9080
A new fluorescent probe for Zn2+, namely, 8-hydroxy-5-N,N-dimethylaminosulfonylquinolin-2-ylmethyl-pendant cyclen (L8), was designed and synthesized (cyclen=1,4,7,10-tetraazacyclododecane). By potentiometric pH, 1H NMR, and UV spectroscopic titrations, the deprotonation constants pKa1-pKa6 of L(8)4 HCl were determined to be <2, <2, <2 (for amino groups of the cyclen and quinoline moieties), 7.19+/-0.05 (for 8-OH of the quinoline moiety), 10.10+/-0.05, and 11.49+/-0.05, respectively, at 25 degrees C with I=0.1 (NaNO3). The results of 1H NMR, potentiometric pH, and UV titrations, as well as single-crystal X-ray diffraction analysis, showed that L8 and Zn2+ form a 1:1 complex [Zn(H-1L8)], in which the 8-OH group of the quinoline ring of L8 is deprotonated and coordinates to Zn2+, in aqueous solution at neutral pH. On addition of one equivalent of Zn2+ and Cd2+, the fluorescence emission of L8 (5 microM) at 512 nm in aqueous solution at pH 7.4 [10 mM HEPES with I=0.1 (NaNO3)] and 25 degrees C increased by factors of 17 and 43, respectively. We found that the cyclen moiety has the unique property of quenching the fluorescence emission of the quinolinol moiety when not complexed with metal cations, but enhancing emission when complexed with Zn2+ or Cd2+. In addition, the Zn2+-L8 complex [Zn(H-1L8)] is much more thermodynamically and kinetically stable (Kd{Zn(H-1L8)}=[Zn2+]free[L8]free/[Zn(H-1L8)]=8 fM at pH 7.4) than the Zn2+ complexes of our previous Zn2+ fluorophores ([Zn(H-1L2)] and [Zn(L3)]). Furthermore, formation of [Zn(H-1L8)] is much faster than those of [Zn(H-1L2)] and [Zn(L3)]. The staining of early-stage apoptotic cells with L8 is also described. 相似文献
10.
Takashi Fukutomi Atsushi Yokota Koji Ishizu 《Journal of polymer science. Part A, Polymer chemistry》1984,22(11):2983-2991
Poly(methyl mehtacrylate)(PMMA) macromers with several vinyl groups at both chain ends were synthesized by the mechanical scission reaction of the main chain in the presence of p-divinylbenzene(p-DVB). The radical copolymerization of this macromer with styrene(St) or MMA was carried out in benzene at 60°C and the reactivity ratio of both monomers (r2) was calculated from a kinetic scheme of copolymerization. As a result, the effect of molecular weight and concentration of macromers was not observed in both copolymerization systems. The value of r2, however, decreased as the number of end vinyl groups in a macromer (N) increased. These results are discussed in some detail as we describe the construction of the kinetic model of copolymerization. 相似文献