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91.
92.
The weakly ionic amphiphilic diblock copolymer polystyrene-b-poly(acrylic acid) was synthesized by nitroxy radical-mediated living radical polymerization with precise control of block length, block ratio, and polydispersity. Systematical surface tension experiments and foam formation observations revealed that this polymer was non-surface active under neutral and alkaline (pH 10) conditions, while it was surface active under an acidic condition (pH 3). This result supports our proposed origin of non-surface activity; the image charge repulsion at the air/water interface is essential in addition to very stable micelle formation in the bulk solution. At a higher pH (pH 12), the polymer showed slight surface activity since the added NaOH played a role as an added salt. The critical micelle concentration (cmc) was estimated by static light scattering. Cmc increased with increasing added salt (NaCl) concentration as was observed for other strongly ionic non-surface-active polymers. Hence, this trend is characteristic for non-surface-active polymers. The pH dependence of cmc was minimum at pH 8–10. Since the acrylic acid block is fully ionized under this condition, the strong image charge repulsion at this condition accelerated micelle formation at a low polymer concentration, which consequently decreased cmc. Micelles in bulk solution were confirmed by dynamic light scattering, and the salt concentration and pH dependencies of the hydrodynamic radius of the micelles were also estimated. The pH-responsive non-surface-active/surface-active transition observed in this study strongly supports the fact that the image charge repulsion is an essential factor for non-surface activity in addition to stable micelle formation in solution. 相似文献
93.
Yuki Hirayama Morimasa Nakamura Takashi Matsuoka 《Surface and interface analysis : SIA》2020,52(12):850-854
Polyoxymethylene (POM, polyacetal) is one of the most popular plastics for machine elements, especially in Japan. However, it is difficult to use it under severe operating conditions such as high speed and high contact pressure. Diamond-like carbon (DLC) coatings were well known to be tribological and functional coatings. However, both POM and DLC coatings are difficult to adhere them each other. In the present paper, DLC coatings are deposited by plasma-based ion implantation and deposition (PBIID) method on POM substrate, and validity of DLC coatings on POM was investigated through friction and mechanical tests. When gas pressure was 0.2 and 0.8 Pa, hardness and adhesion properties of DLC coating deposited under gas pressure of 0.5 Pa were lower compared with under 0.2 and 0.8 Pa. For preparing DLC coatings having hard and good adhesion properties, relatively thin substrate was suitable. A correlation between relative humidity in the laboratory and friction coefficient was confirmed while DLC coatings remain on the substrate. 相似文献
94.
Yulu Jiang Taro Ozaki Mei Harada Tadachika Miyasaka Hajime Sato Kazunori Miyamoto Junichiro Kanazawa Chengwei Liu Jun‐ichi Maruyama Masaatsu Adachi Atsuo Nakazaki Toshio Nishikawa Masanobu Uchiyama Atsushi Minami Hideaki Oikawa 《Angewandte Chemie (International ed. in English)》2020,59(41):17996-18002
Lolitrems are tremorgenic indole diterpenes that exhibit a unique 5/6 bicyclic system of the indole moiety. Although genetic analysis has indicated that the prenyltransferase LtmE and the cytochrome P450 LtmJ are involved in the construction of this unique structure, the detailed mechanism remains to be elucidated. Herein, we report the reconstitution of the biosynthetic pathway for lolitrems employing a recently established genome‐editing technique for the expression host Aspergillus oryzae. Heterologous expression and bioconversion of the various intermediates revealed that LtmJ catalyzes multistep oxidation to furnish the lolitrem core. We also isolated the key reaction intermediate with an epoxyalcohol moiety. This observation allowed us to establish the mechanism of radical‐induced cyclization, which was firmly supported by density functional theory calculations and a model experiment with a synthetic analogue. 相似文献
95.
Yuzuru Uchida Katsumi Onoue Nobuaki Tada Fumio Nagao Hideaki Kozawa Shigeru Oae 《Heteroatom Chemistry》1990,1(4):295-306
Phosphine oxides bearing two or three 2-pyridyl groups react with organometallic reagents affording 2,2′-bipyridyl, 2-substituted pyridines and pyridine in good yields. Phosphonium salts and phosphine oxides, bearing at least two 2-pyridyl or substituted 2-pyridyl groups also give the corresponding 2,2′-bipyridyls and pyridines upon treatment with acid or neutral solvents such as water and alcohols in substantial yields. The 2,2′-bipyridyls are considered to be formed by ligand coupling within the pentacoordinated phosphorus intermediate formed incipiently during the reaction. 相似文献
96.
97.
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
98.
We report the quality anisotropic intermolecular vibrational spectra within the frequency range 0.5-800 cm(-1) of four C(3v) CXY(3) molecular liquids, CHCl(3), CHBr(3), CFBr(3), and CBrCl(3), by means of femtosecond optical-heterodyne-detected Raman-induced Kerr effect spectroscopy. The results show that the first moment of the intermolecular vibrational spectrum is proportional to the square root of the value of the surface tension divided by the liquid density. This implies that the intermolecular vibrational spectrum reflects the bulk properties of the liquids. To understand the molecular-level aspects of the intermolecular vibrational spectra of the liquids, the spectra are compared with the molecular properties such as molecular weight, rotational constants, and bimolecular interaction energy. Overall, the first moment of the spectrum moderately correlates to the inverse square roots of both the molecular weight and the fast rotational constant. Therefore, the molecular properties are responsible for the intermolecular vibrational spectrum. Plots of the first moment of the intermolecular vibrational spectrum vs the square root of the value of the simple bimolecular interaction energy divided by the molecular surface area and the molecular weight show a linear correlation in the case of the oblate symmetric top molecular liquids, CHCl(3), CHBr(3), and CFBr(3). However, CBrCl(3), which is a prolate symmetric top molecular liquid, does not show the same correlation for the oblate molecular liquids. 相似文献
99.
A high‐performance liquid chromatography assay with a triazole‐bonded column for evaluation of d‐amino acid oxidase activity
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Megumi Iwasaki Yoshiyuki Kashiwaguma Chihiro Nagashima Mao Izumi Ayano Uekusa Sumiko Iwasa Mayu Onozato Hideaki Ichiba Takeshi Fukushima 《Biomedical chromatography : BMC》2016,30(3):384-389
Elution profiles of kynurenic acid (KYNA) and 7‐chlorokynurenic acid (Cl‐KYNA) were examined by high‐performance liquid chromatography (HPLC) using a triazole‐bonded stationary phase column (Cosmosil® HILIC) under isocratic elution of a mobile phase consisting of CH3CN–aqueous 10 mm ammonium formate between pH 3.0 and 6.0. The capacity factors of KYNA and Cl‐KYNA varied with both the CH3CN content and the pH of the mobile phase. The elution order of KYNA and Cl‐KYNA was reversed between the CH3CN‐ and H2O‐rich mobile phases, suggesting that hydrophilic interactions and anion‐exchange interactions caused retention of KYNA and Cl‐KYNA in the CH3CN‐ and H2O‐rich mobile phases, respectively. The present HPLC method using a triazole‐bonded column and fluorescence detection (excitation 250 nm, emission 398 nm) was applied to monitor in vitro production of KYNA from d ‐kynurenine (d ‐KYN) by d ‐amino acid oxidase (DAO) using Cl‐KYNA as an internal standard. A single KYNA peak was clearly observed after enzymatic reaction of d ‐KYN with DAO. Production of KYNA from d ‐KYN was suppressed by the addition of commercial DAO inhibitors. The present HPLC method can be used to evaluate DAO activity and DAO inhibitory effects in candidate drugs for the treatment of schizophrenia. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
100.
Tae-Ho Kim Masakazu Saito Masaya Matsuoka Shinya Tsukada Kiyohisa Wada Masakazu Anpo 《Research on Chemical Intermediates》2010,36(5):453-461
It was found that the photoelectrochemical performance and photocatalytic activity of rod-type TiO2 electrodes were affected by various post-calcination treatments, for example, calcination in NH3 or under vacuum. Post-calcination treatment in NH3 at 773 K was particularly effective in increasing the photoelectrochemical performance and photocatalytic activity of rod-type
TiO2 electrodes. A unique photoelectrochemical circuit was constructed by connecting a rod-type TiO2 electrode to a Pt electrode through a silicon solar cell in which the negative bias was applied on the rod-type TiO2 electrode. It was found that the photoelectrochemical circuit can effectively oxidize ethanethiol in water into CO2. 相似文献