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21.
Toshimasa Hashimoto Tetsuya Sakai Seizo Miyata 《Journal of Polymer Science.Polymer Physics》1978,16(11):1965-1971
Thermally stimulated current (TSC) has been observed in extended-chain crystals of polyethylene above room temperature. The TSC spectra exhibit two current peaks of opposite polarity. The peaks were separated into separate components by curve fitting. The position of the negative peak, which appears at 123°C, is independent of charging conditions. The positive current increases after γ irradiation or aging of the samples. 相似文献
22.
Yuko Okamoto Toshimasa Tanaka Hironori Kokubo 《Journal of computer-aided molecular design》2010,24(8):699-712
We performed replica-exchange molecular dynamics (REMD) simulations of six ligands to examine the dependency of their free
energy landscapes on charge parameters and solvent models. Six different charge parameter sets for each ligand were first
generated by RESP and AM1-BCC methods using three different conformations independently. RESP charges showed some conformational
dependency. On the other hand, AM1-BCC charges did not show conformational dependency and well reproduced the overall trend
of RESP charges. The free energy landscapes obtained from the REMD simulations of ligands in vacuum, Generalized-Born (GB),
and TIP3P solutions were then analyzed. We found that even small charge differences can produce qualitatively different landscapes
in vacuum condition, but the differences tend to be much smaller under GB and TIP3P conditions. The simulations in the GB
model well reproduced the landscapes in the TIP3P model using only a fraction of the computational cost. The protein-bound
ligand conformations were rarely the global minimum states, but similar conformations were found to exist in aqueous solution
without proteins in regions close to the global minimum, local minimum or intermediate states. 相似文献
23.
Copper-Free Sonogashira coupling in water with an amphiphilic resin-supported palladium complex 总被引:1,自引:0,他引:1
The palladium-catalyzed coupling reaction of aryl halides with terminal alkynes, the Sonogashira coupling, took place in water under copper-free conditions by use of an amphiphilic polystyrene-poly(ethylene glycol) (PS-PEG) resin-supported palladium-phosphine complex to give the corresponding aryl-substituted alkynes in high yields. The PS-PEG resin-supported palladium catalyst was recovered by simple filtration and reused four times without any loss of catalytic activity. 相似文献
24.
Shogo Mitsuhashi Junko Kawai Tomofumi Santa Toshimasa Toyo’oka 《Analytica chimica acta》2006,562(1):36-43
Kynurenic acid (KYNA), an endogenous antagonist of ionotropic glutamate and α7 nicotinic receptors, was fluorometrically determined by column-switching high-performance liquid chromatography (HPLC) with fluorescence detection. The HPLC system consists of two octadecyl silica (ODS) columns, both of which are connected with an anion-exchange column (trapping column). Following sample injection onto the HPLC column, KYNA was separated on the first ODS column with a mobile phase of H2O/acetonitrile (95/5) containing 0.1% acetic acid. The peak fraction of KYNA was trapped on the anion-exchange column by changing the position of a six-port valve and then introduced into the second ODS column. Subsequently, KYNA was detected fluorometrically as a fluorescence complex formed with zinc ion which was pumped constantly. Instrumental limit of detection was approximately 0.16 nM, which corresponded to 8.0 fmol (per 50 μl injection, signal to noise ratio 3), and the limit of quantification was 0.53 nM (signal to noise ratio 10). Intra- and inter-day relative standard deviations were 1.1-3.9% (n = 3) and 3.0-5.3% (n = 3), respectively. The peak of KYNA in rat plasma was clearly detected by the proposed column-switching HPLC system after a facile pretreatment procedure. Intra- and inter-day relative mean errors were −1.6-1.4% (n = 3) and −2.4 to −0.4% (n = 3), respectively, with a satisfactory precision (within 5.0%). A calibration curve for the determination of KYNA showed a good linearity (r2 > 0.999) in the range of 25-200 nM. The KYNA concentrations in the plasma of male Sprague-Dawley rats (8-week-old) were 44 ± 5.5 nM (mean ± S.E., n = 5). In ketamine-treated rats, which are animal models of schizophrenia, the plasma KYNA concentrations were significantly increased compared with those in the control rats (p < 0.05). 相似文献
25.
4-(3,17Beta-dihydroxyestra-1,3,5(10)-trien-6alpha- and 6beta-yl)amino-7-nitro-2,1,3-benzoxadiazoles have been synthesized and characterized as fluorescent probes for use in a receptor assay and/or a homogeneous immunoassay for estradiol. The fluorescence intensities are strongly dependent upon the solvent polarity used. The intensities in water were reduced to less than 1% of those in ethyl acetate, and a blue shift was also observed in polar solvents. The quenched fluorescence in aqueous solution was recovered by adding bovine serum albumin or an anti-estradiol antibody. Adding intact estradiol inhibited the fluorescence recovered by the antibody. 相似文献
26.
Akihito Kitajima Takeshi Kashirajima Takao Minamizawa Hiroyasu Sato Kazuo Iwaki Taisuke Ueda Yoshio Kimura Toshimasa Toyo'oka Tamio Maitani Rieko Matsuda Yuzuru Hayashi 《Analytical sciences》2007,23(9):1077-1080
The stochastic properties of baseline noise in HPLC systems with a UV photo-diode array, photo-multiplier and gamma-ray detector were examined by dividing the noise into auto-correlated random process (Markov process) and an independent process (white noise). The present work focused on the effect of the stochastic noise properties on a theoretical estimation of the standard deviation (SD) of area measurements in instrumental analyses. An estimation theory, called FUMI theory (Function of Mutual Information), was taken as an example. A computer simulation of noise was also used. It was shown that the reliability (confidence intervals) of theoretical SD estimates mainly depends on the following factors: the ratio of the white noise and Markov process occurring in the baselines; the number of data points used for the estimation; the width of a target peak for which the SD is estimated. 相似文献
27.
Jun Zhe Min Toshimasa Toyooka Hiroki Kawanishi Takeshi Fukushima Masaru Kato 《Analytica chimica acta》2005,550(1-2):173-181
Several fluorescent asparaginyl-N-acetyl-d-glucosamines (Asn-GlcNAcs), i.e., DBD-Asn-GlcNAc, NBD-Asn-GlcNAc, NDA-Asn-GlcNAc, PS-Asn-GlcNAc, FITC-Asn-GlcNAc, DMEQ-Asn-GlcNAc and DBD-PZ-Boc-Asn-GlcNAc, were synthesized as the acceptors for the resolution of oligosaccharides in glycopeptides. The resolution of oligosaccharides is based on the transglycosylation reaction with end-β-N-acetylglucosaminidase (Endo-M), isolated from Mucor hiemalis. The synthesis of each fluorescent acceptor was carried out in a one-pot reaction of Asn-GlcNAc and the corresponding fluorescent tagging reagent. The transglycosylation reaction using Endo-M proceeds at RT in neutral phosphate buffer (pH 6.0) and reached maxima at around 30 min. When Fmoc-Asn-GlcNAc (acceptor) was enzymatically reacted with Disialo-Asn (donor) in the presence of Endo-M, the ratio of Disialo-Asn-Fmoc (transglycosylation product) was almost comparable with the decreasing ratio of Fmoc-Asn-GlcNAc. Therefore, the transglycosylation activity of Endo-M from Disialo-Asn (donor) and fluorescent-Asn-GlcNAc (acceptor) was calculated from the decreasing ratio of fluorescent-Asn-GlcNAc. The order was NDA-Asn-GlcNAc > DBD-Asn-GlcNAc Fmoc-Asn-GlcNAc > NBD-Asn-GlcNAc DMEQ-Asn-GlcNAc > DNS-Asn-GlcNAc > PS-Asn-GlcNAc > FITC-Asn-GlcNAc. On the other hand, the activity with a fluorescent acceptor (DBD-PZ-Boc-Asn-GlcNAc), labeled to a carboxylic acid group in the Asn residue, was the strongest among the synthesized acceptors. 相似文献
28.
Sinnott JM Gonzales CL Masood AF Ishihara T 《The Journal of the Acoustical Society of America》2007,121(6):3846-3857
Humans were trained to categorize problem non-native phonemes using an animal psychoacoustic procedure that trains monkeys to greater than 90% correct in phoneme identification [Sinnott and Gilmore, Percept. Psychophys. 66, 1341-1350 (2004)]. This procedure uses a manual left versus right response on a lever, a continuously repeated stimulus on each trial, extensive feedback for errors in the form of a repeated correction procedure, and training until asymptotic levels of performance. Here, Japanese listeners categorized the English liquid contrast /r-l/, and English listeners categorized the Middle Eastern dental-retroflex contrast /d-D/. Consonant-vowel stimuli were constructed using four talkers and four vowels. Native listeners and phoneme contrasts familiar to all listeners were included as controls. Responses were analyzed using percent correct, response time, and vowel context effects as measures. All measures indicated nativelike Japanese perception of /r-l/ after 32 daily training sessions, but this was not the case for English perception of /d-D/. Results are related to the concept of "robust" (more easily recovered) versus "fragile" (more easily lost) phonetic contrasts [Burnham, Appl. Psycholing. 7, 207-240 (1986)]. 相似文献
29.
Toshiki Mochizuki Takahiro TakayamaKenichiro Todoroki Koichi InoueJun Zhe Min Toshimasa Toyo’oka 《Analytica chimica acta》2015
A novel triazine-type chiral derivatization reagent, i.e., (S)-2,5-dioxopyrrolidin-1-yl-1-(4,6-dimethoxy-1,3,5-triazin-2-yl) pyrrolidine-2-carboxylate (DMT-(S)-Pro-OSu), was developed for the highly sensitive and selective detection of chiral amines and amino acids by UPLC–MS/MS analysis. The enantiomers of amino acids were easily labeled with the reagents at room temperature within 40 min in an alkaline medium containing triethylamine. The diastereomers derived from proteolytic amino acids, except serine, were well separated under isocratic elution conditions by reversed-phase chromatography using an ODS column (Rs = 1.2–9.0). dl-Serine was separated by use of an ADME column which has relatively higher polar surface than the conventional ODS column. The characteristic product ions, i.e., m/z 195.3 and m/z 209.3, were detected from all the diastereomers by the collision-induced dissociation of the protonated molecule. A highly sensitive detection on the amol–fmol level was obtained from the selected reaction monitoring (SRM) chromatogram. The chiral amines (e.g., adrenaline and noradrenaline) labeled with DMT-(S)-Pro-OSu were also well separated and sensitively detected by the present procedure. The method using DMT-(S)-Pro-OSu was used for the determination of dl-amino acids in the human saliva from healthy volunteers. Various l-amino acids were identified in the saliva. Furthermore, d-alanine (d-Ala) and d-proline (d-Pro) were also detected in relatively high concentrations (>5%). The ratio was higher in male saliva than in female saliva. However, the difference in the ratio of d-Ala for one day was not very high and the effect of foods and beverage seemed to be negligible. Based on the results using l-Ala-d3, the d-Ala in saliva seemed to be produced due to the racemization with some enzymes such as racemase. The racemization reaction was reversible, i.e., d-Ala-d3 was also racemized to l-Ala-d3 in saliva. Thus, care should be taken during the analysis of dl-amino acids in saliva. The present method using DMT-(S)-Pro-OSu may be applicable for the determination of chiral amine metabolomics, because the resulting derivatives produce the same product ions without relation to the compounds and show highly sensitive detection in the SRM mode of MS/MS. Consequently, DMT-(S)-Pro-OSu seems to be a useful chiral derivatization reagent for the determination of amines and amino acids in biological samples. 相似文献
30.
The Epstein?CBarr virus (EBV) is associated with a variety of malignancies and chronic active EBV infection is a severe systemic disease associated with high rates of mortality and morbidity. In this paper, the dynamics of the interaction of EBV-expressed latent membrane protein 1 (LMP1) with cellular signaling intermediate tumor necrosis factor receptor (TNFR)-associated factor 3 (TRAF3) is simulated using standard classical molecular dynamics (MD) protocols. For comparison, the dynamics of the interaction of TRAF3 with CD40, a TNFR mimicked by LMP1 to effect EBV infection is also calculated under similar conditions. Essential dynamics (ED) analysis is carried out to identify important degrees of vibrational freedom that relate to protein function and virus infection. Both the MD simulation and ED analysis reveal novel interactions that help explain the structural decoy action of LMP1 over CD40. These interactions involve the consensus sequence PXQXTXX shared by CD40 and LMP1. In LMP1, we have found novel interaction of Asp 209 with TRAF3 and the interaction is crucial although the adjacent Asp 210 was suggested to be essential by the X-ray analysis. In CD40, it is found that the hairpin formation is not indispensable for the interaction with TRAF3. 相似文献