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151.
T. Tatsumi T. Fukushima K. Imada M. Takayanagi 《Journal of Macromolecular Science: Physics》2013,52(3):459-483
The effect of heat treatment of trans-1,4-polybutadiene single crystals prepared from dilute benzene solution was studied by dilatometry, X-ray diffraction, and dynamic viscoelastic measurement. The crystal transformation temperature of the single crystal is 55.5[ddot]C, 20[ddot]C lower than that of the bulk crystallized sample. After heat treatment of the single crystal above 55.5[ddot]C, their crystal transformation temperature increases to 69.5[ddot]C. At the same time, thickening of the lamellae suddenly occurs and the viscoelastic primary absorption observed in the single crystal mat disappears. It is suggested that this means that the amorphous region attached to the single crystal rapidly crystallized above this temperature, in particular the loose loops attached to the end surface of the crystal are dragged into the crystalline phase to form tight loops as a result of the sliding diffusion of molecules along their axes. This is accompanied by the sudden thickening of the lamellae at the crystal transformation temperature. These observations confirmed more thoroughly our previous prediction that the single crystal of trans-1, 4-polybutadiene, as formed, contains loose loops. The thickening phenomena and the change in the crystal transformation temperature of the trans-1,4-polybutadiene single crystal by heat treatment are also discussed from the thermodynamic viewpoint. 相似文献
152.
M. Tanaka H. Kohri T. Ohta M. Yosoi M. Fujiwara K. Ueda S. Imoto K. Takamatsu J. -P. Didélez G. Frossati A. de Waard Yu. Kiselev S. Makino H. Fujimura K. Fukushima S. Fukushima H. Kondoh 《Physics of Particles and Nuclei》2013,44(6):959-963
The project in producing the hyperpolarized 3He and 19F are addressed in pursuit of radiation free medical diagnosis. The program for production of the hyperpolarized 3He by the brute force method with the Pomeranchuk cooling and the rapid melting of the solid 3He started a few years ago, and is still on the way, while a new program for production of the hyperpolarized 19F by means of the PHIP (ParaHydrogen Induced Polarization) has just got started. Particular attention is placed upon a new idea of the hyperpolarization catalyst to be used for 19F. 相似文献
153.
A diphenylanthracene-based diamidine (1a) fluorescent probe for the detection of dicarboxylic acids has been designed and synthesized, which has an extended π-conjugation rather than a simple anthracene ring, in order to observe highly different fluorescence wavelengths after complex formation with dicarboxylic acids. The fluorescence spectra of the mixed solution of the diamidine 1a and carboxylic acids showed two different fluorescence bands, which corresponded to the complex formation (amidinium-carboxylate formation, λem?=?450?nm, light blue color) and dissociated amidinium formation (λem?=?510?nm as a broad band, green color). The complexed and dissociated states were confirmed by DOSY NMR and TD-DFT calculations. These different fluorescence wavelengths may come from the differences in the dihedral angles between the phenyl rings at the 1,8-position and anthracene ring (difference in π-conjugation) of 1a under complex formation and dissociated amidinium formation. The proposed mechanism for the observation of the different fluorescence wavelengths (complex formation and amidinium formation) was also confirmed by the fluorescence study of diamidine 1b which causes restricted rotation of the phenyl rings by substitution of the steric methyl groups, and observed the same fluorescence spectra for the complex formation and amidinium formation (400, 420, 450?nm as a vibrational structure of anthracene ring). These fluorescence characteristics of the diamidine 1a are also applicable for the detection of α,ω?dicarboxylic acids. 相似文献
154.
Satomi Fukushima Minoru Ashizawa Susumu Kawauchi Tsuyoshi Michinobu 《Helvetica chimica acta》2019,102(4)
Octadehydrodibenzo[12]annulenes (DBAs), readily available by the oxidative acetylenic coupling of 1,2‐diethynylbenzene derivatives, were reacted with organic azides. As compared to the well‐known strain‐promoted azide‐alkyne cycloaddition (SpAAC) of 5,6,11,12‐tetradehydrodibenzo[a,e][8]annulene, the reactivity of the DBA alkynes was lower due to the lower strain energy. However, the regioselective double azide addition occurred without any side reactions under mild conditions, yielding bis‐triazole products. The structures of the products were confirmed by an X‐ray crystal structure analysis, and the reaction mechanism was studied by 1H‐NMR spectroscopy and computational studies. It was also found that the DBAs were hardly fluorescent, while the bis‐triazole products showed a green fluorescence with quantum yields up to 5.1 %. Finally, the new strain‐promoted double azide addition to the DBAs was used for step‐growth polymerization, successfully producing a high molecular weight triazole polymer. 相似文献
155.
Shotaro Hayashi Minami Sakamoto Fumitaka Ishiwari Takanori Fukushima Shin-ichi Yamamoto Toshio Koizumi 《Tetrahedron》2019,75(8):1079-1084
Here we report the facile derivatization of a cyano-substituted stilbene into higher π-extended analogues. The cyano-substituted stilbene, which serves as a synthetic scaffold, has a bromo group and a formyl group on its 4- and 4′-position of the phenylene rings and thus readily undergoes selective transformation into other functional groups using various simple organic reactions. The resultant π-conjugated molecules that contain a cyano-substituted stilbene skeleton exhibit fluorescence in solution and in the solid state. 相似文献
156.
The anionic organic dye, zincon, was found to be a colorimetric probe for spermine and spermidine at pH 4.0 in pure aqueous solution through its aggregation by electrostatic interactions with them. The addition of spermine and spermidine led to bathochromic shifts with color changes from yellow to purple and dark brown, respectively, while other amines and basic amino acids induced no or minimal spectral and color changes. From Job’s plot and titration experiments, zincon interacted with spermine (+4 charges) and spermidine (+3 charges) in 4:1 and 3:1 stoichiometric ratios, respectively, indicating that each positive charge was bound to one zincon molecule. The detection limits were determined to be 25.1 for spermine and 30.7 nM for spermidine, which were sufficient below the critical concentration for cancer diagnosis. The results indicated that zincon can be a good candidate for simple, convenient colorimetric detection of spermine and spermidine in aqueous solution. 相似文献
157.
We investigate the effect of a magnetic field on cold dense quark matter using an effective model with four-Fermi interactions. We find that the gap parameters representing the predominant pairing between the different quark flavors show oscillatory behavior as a function of the magnetic field. We point out that due to electric and color neutrality constraints the magnetic fields as strong as presumably existing inside magnetars might induce significant deviations from the gap structure at a zero magnetic field. 相似文献
158.
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
159.
We developed a novel derivatization reagent, (2R)-2,5-dioxopyrrolidin-1-yl-2,5,7,8-tetramethyl-6-(tetrahydro-2H-pyran-2-yloxy)chroman-2-carboxylate (NPCA), for electrochemical (EC) detection in HPLC. NPCA was synthesized from (R)-(+)-6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (alpha-CA), which exhibits intense EC response. NPCA successfully yielded alpha-CA derivatives of primary amines by a two-step derivatization procedure. Following pre-column derivatization with NPCA, a simultaneous determination of alpha-CA derivatives of neuroactive monoamines [dopamine (DA), epinephrine, and 5-hydroxytryptamine (5-HT)], their monoamine oxidase metabolites (3,4-dihydroxyphenylacetic acid, homovanillic acid, and 5-hydroxyindole-3-acetic acid) and their catechol-O-methyltransferase metabolites [3-methoxytyramine (3-MT) and normetanephrine (NMN)] was completely achieved using our HPLC-EC method. Using an HPLC equipped with coulometric electrode-array detection system, the resultant alpha-CA derivatives of NMN, 5-HT, DA and 3-MT showed intense EC responses, that were approximately 1.3, 1.4, 1.1 and 1.4-fold higher than the corresponding native forms, respectively. The detection limits were in the range of approximately 16-60 fmol on column (signal-to-noise ratio 3). The proposed HPLC method was applied to determine 5-HIAA, HVA, alpha-CA-5-HT and alpha-CA-DA in rat urine. As a consequence, these analytes were successfully determined with satisfactory precisions. 相似文献
160.
Fukushima T Arai K Tomiya M Mitsuhashi S Sasaki T Santa T Imai K Toyo'oka T 《Biomedical chromatography : BMC》2008,22(1):100-105
N-acetyl-L-aspartic acid (NAA) is an endogenous compound, and its brain concentration is suggested to be altered in neurological disorders. In the present study, a fluorescence determination method for NAA was developed by employing reversed-phase high-performance liquid chromatography (HPLC) with pre-column fluorescence derivatization using 4-N,N-dimethylaminosulfonyl-7-N-(2-aminoethyl)amino-2,1,3-benzoxadiazole (DBD-ED). Using methylsuccinic acid as the internal standard, a linear calibration curve for NAA was constructed in the range 125-1000 microM (n=3). The detection limit on the column was approximately 5.0 fmol (signal-to-noise ratio 3). The proposed HPLC method was applied to determine NAA in the rat cerebrum homogenate. Cerebrum NAA was successfully determined using 10 microL of the homogenate, and the validation data for the proposed HPLC method demonstrated satisfactory results. Intra- and inter-day precision and accuracy were within 1.1-7.0 and -8.1-6.3%, respectively. The concentration of NAA in the male rat cerebrum (13 weeks old) was 84+/-4.6 micromol/mg protein (n=3). 相似文献