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81.
82.
The polarizable continuum model (PCM) for describing the solvent effect was combined with the fragment molecular orbital-based time-dependent density functional theory (TDDFT). Several levels of the many-body expansion were implemented, and the importance of the many-body contributions to the singlet-excited states was discussed. To calibrate the accuracy, we performed a number of the model calculations using our method and the regular TDDFT in solution, applying them to phenol and polypeptides at the long-range corrected BLYP/6-31G* level. It was found that for systems up to 192 atoms the largest error in the excitation energy was 0.006 eV (vs. the regular TDDFT/PCM of the full system). The solvent shifts and the conformer effects were discussed, and the scaling was found to be nearly linear. Finally, we applied our method to the lowest singlet excitation of the photoactive yellow protein (PYP) in aqueous solution and determined the excitation energy to be in reasonable agreement with experiment. The excitation energy analysis provided the contributions of individual residues, and the main factors as well as their solvent shifts were determined. 相似文献
83.
Partis L Burns M Chiba K Corbisier P Gancberg D Holden MJ Wang J Liu QY Okunishi T Yang I Vonsky M Emslie KR 《Electrophoresis》2007,28(18):3193-3200
A simple amplified fragment length polymorphism (AFLP) model, using the bacteriophage lambda genome, was developed to test the reproducibility of this technique in an international comparative study. Using either non-selective or selective primers, nine fragments or subsets of two or three fragments, respectively, were predicted using in silico software. Under optimized conditions, all predicted fragments were experimentally generated. The reproducibility of the AFLP model was tested by submitting both "unknown" DNA template that had been restricted and ligated with AFLP linkers (R/L mixture) and corresponding primer pairs to nine laboratories participating in the study. Participants completed the final PCR step and then used either slab gel electrophoresis or CE to detect the AFLP fragments. The predicted fragments were identified by the majority of participants with size estimates consistently up to 3 base pair (bp) larger for slab gel electrophoresis than for CE. Shadow fragments, 3 bp larger than the predicted fragments, were often observed by study participants and organizers. The nine AFLP fragments exhibited relative intensities ranging from less than 3% to 22% and, apart from the two weakest fragments, with a % CV of 16 to 25. Fragments containing the highest guanine-cytosine (GC) content of 50-56% showed the greatest stability in the AFLP profiles. 相似文献
84.
Inagaki K Narukawa T Yarita T Takatsu A Okamoto K Chiba K 《Analytical and bioanalytical chemistry》2007,389(3):691-696
A coprecipitation method using sample constituents as carrier precipitants was developed that can remove molybdenum, which
interferes with the determination of cadmium in grain samples via isotope dilution inductively coupled plasma mass spectrometry
(ID-ICPMS). Samples were digested with HNO3, HF, and HClO4, and then purified 6 M sodium hydroxide solution was added to generate colloidal hydrolysis compounds, mainly magnesium hydroxide.
Cadmium can be effectively separated from molybdenum because the cadmium forms hydroxides and adsorbs onto and/or is occluded
in the colloid, while the molybdenum does not form hydroxides or adsorb onto the hydrolysis colloid. The colloid was separated
by centrifugation and then dissolved with 0.2 M HNO3 solution to recover the cadmium. The recovery of Cd achieved using the coprecipitation was >97%, and the removal efficiency
of Mo was approximately 99.9%. An extremely low procedural blank (below the detection limit of ICPMS) was achieved by purifying
the 6 M sodium hydroxide solution via Mg coprecipitation using Mg(NO3)2 solution. The proposed method was applied to two certified reference materials (NIST SRM 1567a wheat flour and SRM 1568a
rice flour) and CCQM-P64 soybean powder. Good analytical results with small uncertainties were obtained for all samples. This
method is simple and reliable for the determination of Cd in grain samples by ID-ICPMS.
Figure Overview of a coprecipitation method using sample constituents 相似文献
85.
The temperature dependence of the dynamic shear modulus, strain optical coefficient, DC conductivity, and complex dielectric spectrum of κ- and ι-carrageenan aqueous solutions with K, Ca, Cs, and Na were measured in order to clarify the formation process of the cross-linking region and the gel network structure. From the correlation analysis between the shear modulus and the strain optical coefficient, we found that the stress inducing unit orientation increases with decreasing temperature, which strongly suggests that the branching number in a cross-linking region increases with decreasing temperature, which depends on counterion species. In terms of the correlation parameters, an increasing scheme of the branching number depends on counterion species. Just below the coil-helix transition temperature, dielectric relaxation arises, with relaxation time ∼100μs and relaxation strength ∼103. Dielectric relaxation can be assigned to the counterion fluctuation in the parallel direction to the helical axis. The fluctuation distance of the counterion estimated from the relaxation time increases sharply in the initial stage of gelation and gradually reaches a constant value. We concluded that the longitudinal length of the aggregated region increases sharply at the initial state of gelation while the number of helical molecules bundled in a cross-linking region increases successively with decreasing temperature. 相似文献
86.
A protocol for the synthesis of α-tertiary amines was developed by iterative addition of carbon nucleophiles to N,N-dialkyl carboxamides. Nucleophilic 1,2-addition of organolithium reagents to carboxamides forms anionic tetrahedral carbinolamine (hemiaminal) intermediates, which are subsequently treated with bromotrimethylsilane (Me3SiBr) followed by organomagnesium (Grignard) reagents, organolithium reagents or tetrabutylammonium cyanide, affording α-tertiary amines. Employment of (trimethylsilyl)methylmagnesium bromide as the 2nd nucleophile allowed for aza-Peterson olefination of the resulting α-tertiary (trimethylsilyl)methylamines with acidic work-up, resulting in the formation of 1,1-diarylethylenes.We herein report a concise protocol for iterative addition of carbon nucleophiles to N,N-dialkyl carboxamides for the synthesis of α-tertiary amines. 相似文献
87.
88.
Takayuki Muro Yukako Kato Toyohiko Kinoshita Yoshio Watanabe 《Journal of synchrotron radiation》2009,16(4):595-596
A video camera system for observing a sample from the direction of an incident soft X‐ray beam has been developed. The sample is seen via two reflecting mirrors. The first mirror, which has a hole to allow the soft X‐ray beam to pass through, is set on the beam axis in a vacuum. The second mirror is used to cancel out the mirror inversion of the image. This camera system is used for efficient positioning of samples in a soft X‐ray beam. 相似文献
89.
Chiba J Iimura S Yoneda Y Sugimoto Y Horiuchi T Muro F Ochiai Y Ogasawara T Tsubokawa M Iigou Y Takayama G Taira T Takata Y Yokoyama M Takashi T Nakayama A Machinaga N 《Chemical & pharmaceutical bulletin》2006,54(11):1515-1529
A novel series of benzoic acid derivatives as VLA-4 antagonists were synthesized. Optimization, focusing on activity and lipophilicity needed for cell permeability, resulted in the identification of 15b and 15e with good activity (IC50 = 1.6 nM each) and moderate lipophilicity (Log D = 2.0, 1.8). Furthermore, 15e demonstrated efficacy in murine asthma model by an oral dose of 30 mg/kg. 相似文献
90.
Yuka Akimura Toshiki Maruyama Naotaka Yoshinaga Satoshi Chiba 《Acta Physica Hungarica A》2006,27(2-3):355-358
We study the hadron-quark phase transition in a molecular dynamics (MD) of quark degrees of freedom. The hadron state at low density and temperature, and the deconfined quark state at high density and temperature are observed in our model. We investigate the equations of state and draw the phase diagram at wide baryon density and temperature range. We also discuss the transport property, e.g. viscosity, of $q\bar q$ matter. It is found that the ratio of the shear viscosity to the entropy density is less than one for quark matter. 相似文献