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991.
Takeshi Yamada Takashi Kikuchi Reiko Tanaka Atsushi Numata 《Tetrahedron letters》2012,53(23):2842-2846
Halichoblelide B (1) and C (2), novel macrolides with potent cytotoxicity against tumor cells in culture, have been isolated from a strain of Streptomyces hygroscopicus originally derived from the marine fish Halichoeres bleekeri, and their absolute stereostructures have been elucidated on the basis of spectroscopic analyses using 1D and 2D NMR techniques and chemical transformations. These compounds exhibited significant cytotoxicity against human cancer cell lines. 相似文献
992.
The iron mixed-valence complex (n-C(3)H(7))(4)N[Fe(II)Fe(III)(dto)(3)] exhibits a novel type of phase transition called charge-transfer phase transition (CTPT), where the thermally induced electron transfer between Fe(II) and Fe(III) occurs reversibly at ~120 K, in addition to the ferromagnetic phase transition at T(C) = 7 K. To investigate the mechanism of the CTPT, we have synthesized a series of magnetically diluted complexes (n-C(3)H(7))(4)N[Fe(II)(1-x)Zn(II)(x)Fe(III)(dto)(3)] (dto = C(2)O(2)S(2); x = 0-1), and carried out magnetic susceptibility and dielectric constant measurements and (57)Fe M?ssbauer spectroscopy. With increasing Zn(II) concentration (x), the CTPT is gradually suppressed and disappears at x ≈ 0.13. On the other hand, the ferromagnetic transition temperature (T(C)) is initially enhanced from 7 K to 12 K between x = 0.00 and 0.05, despite the nonmagnetic nature of Zn(II) ions, and then it decreases monotonically from 12 K to 3 K with increasing Zn(II) concentration. This anomalous dependence of T(C) on Zn(II) concentration is related to a change in the spin configuration of the ferromagnetic state caused by the partial suppression of the CTPT. 相似文献
993.
Lopes IC Santos PV Diculescu VC Peixoto FM Araújo MC Tanaka AA Oliveira-Brett AM 《The Analyst》2012,137(8):1904-1912
Microcystins (MCs) are cyclic hepatotoxic heptapeptides produced by certain strains of freshwater cyanobacteria toxic for humans and animals. The electrochemical behaviour of microcystin-LR (MC-LR) at a glassy carbon electrode (GCE) was investigated using cyclic voltammetry (CV), square wave voltammetry (SWV) and differential pulse voltammetry (DPV). The oxidation of MC-LR is a diffusion-controlled irreversible and pH-independent process that occurs with the transfer of only one electron and does not involve the formation of any electroactive oxidation product. Upon incubation in different pH electrolytes, homogeneous degradation of MC-LR in solution was electrochemically detected by the appearance of a new oxidation peak at a lower potential. The electrochemical behaviour of chemically degraded MC-LR is an irreversible, pH-dependent process, and involves the formation of two redox products that undergo reversible oxidation. The formation of degradation products of MC-LR was confirmed by HPLC with UV detection at room temperature. Experiments were also carried out in solutions containing constituent MC-LR amino acids, which enabled the understanding of the MC-LR electron transfer reaction and degradation. An oxidation mechanism for MC-LR is proposed. 相似文献
994.
We present a simple and exact numerical approach to compute the free energy contribution δμ in solvation due to the electron density polarization and fluctuation of a quantum-mechanical solute in the quantum-mechanical/molecular-mechanical (QM/MM) simulation combined with the theory of the energy representation (QM/MM-ER). Since the electron density fluctuation is responsible for the many-body QM-MM interactions, the standard version of the energy representation method cannot be applied directly. Instead of decomposing the QM-MM polarization energy into the pairwise additive and non-additive contributions, we take sum of the polarization energies in the QM-MM interaction and adopt it as a new energy coordinate for the method of energy representation. Then, it is demonstrated that the free energy δμ can be exactly formulated in terms of the energy distribution functions for the solution and reference systems with respect to this energy coordinate. The benchmark tests were performed to examine the numerical efficiency of the method with respect to the changes in the individual properties of the solvent and the solute. Explicitly, we computed the solvation free energy of a QM water molecule in ambient and supercritical water, and also the free-energy change associated with the isomerization reaction of glycine from neutral to zwitterionic structure in aqueous solution. In all the systems examined, it was demonstrated that the computed free energy δμ agrees with the experimental value, irrespective of the choice of the reference electron density of the QM solute. The present method was also applied to a prototype reaction of adenosine 5'-triphosphate hydrolysis where the effect of the electron density fluctuation is substantial due to the excess charge. It was demonstrated that the experimental free energy of the reaction has been accurately reproduced with the present approach. 相似文献
995.
Ikeda-Ohno A Tsushima S Hennig C Yaita T Bernhard G 《Dalton transactions (Cambridge, England : 2003)》2012,41(24):7190-7192
Primary aquo species of tetravalent cerium (Ce(IV)) in perchloric acid has been identified as a single oxo-bridging dinuclear complex, not a mononuclear one, by extended X-ray absorption fine structure (EXAFS) spectroscopy combined with density functional theory (DFT) calculations. 相似文献
996.
Morisaki Y Ueno S Saeki A Asano A Seki S Chujo Y 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(14):4216-4224
[2.2]Paracyclophane-based through-space conjugated oligomers and polymers were prepared, in which poly(p-arylene-ethynylene) (PAE) units were partially π-stacked and layered, and their properties in the ground state and excited state were investigated in detail. Electronic interactions among PAE units were effective through at least ten units in the ground state. Photoexcited energy transfer occurred from the stacked PAE units to the end-capping PAE moieties. The electrical conductivity of the polymers was estimated using the flash-photolysis time-resolved microwave conductivity (FP-TRMC) method and investigated together with time-dependent density functional theory (TD-DFT) calculations, showing that intramolecular charge carrier mobility through the stacked PAE units was a few tens of percentage larger than through the twisted PAE units. 相似文献
997.
Hiroyuki Nasu Tomohiro Ito Yuki Nagaike Sachio Ninagawa Tomohide Hatasa Daisuke Hirota Kenichi Hasegawa Tadanori Hashimoto Atsushi Ishihara 《Journal of Non》2011,357(3):1013-1015
Second harmonic generation (SHG) was observed from halide, in specific, chlorine or bromine-containing tellurite glasses. The magnitude of SHG increased with increasing halides concentration and poling time. Although the mechanism of SHG is still controversial, it is generally accepted that the idea of the deficiency of cations near the anode side cause SHG. However, in the preset oxyhalide glass system without any singly positive charge cation, the polishing of the anode side showed no effect on SHG. On the other hand, the polishing of the cathode side significantly decreased the magnitude of SHG in the present alkali-free oxyhalide glasses. Therefore, the SHG mechanism in the present oxyhalide glass systems is made evident in which the movement of anions results in an anion-deficient layer near the cathode side. 相似文献
998.
Atsushi Hosaka Tetsuo Hyodo Daisuke Jido Hideko Nagahiro Kanabu Nawa Shunsuke Ohkoda Sho Ozaki Yasuhiro Yamaguchi Shigehiro Yasui 《Few-Body Systems》2013,54(1-4):19-24
In hadron resonances different structures of hadronic composite (molecule) and elementary (quark-intrinsic) natures may coexist. We sketch discussions based on our previous publications on the origin of hadron resonances (Hyodo et al. Phys. Rev. C 78:025203, 2008) on exotic ${\bar D (B)}$ meson–nucleons as candidates of hadronic composites (Yamaguchi et al. Phys. Rev. D 84:014032, 2011) and on a 1 for the coexistence/mixing of the two different natures (Nagahiro et al. Phys. Rev. D 83:111504, 2011). 相似文献
999.
Koji Kamagata Hiroyuki Tomiyama Yumiko Motoi Masayoshi Kano Osamu Abe Kenji Ito Keigo Shimoji Michimasa Suzuki Masaaki Hori Atsushi Nakanishi Ryohei Kuwatsuru Keisuke Sasai Shigeki Aoki Nobutaka Hattori 《Magnetic resonance imaging》2013
Objective
The pathological changes in Parkinson disease begin in the brainstem; reach the limbic system and ultimately spread to the cerebral cortex. In Parkinson disease (PD) patients, we evaluated the alteration of cingulate fibers, which comprise part of the limbic system, by using diffusional kurtosis imaging (DKI).Methods
Seventeen patients with PD and 15 age-matched healthy controls underwent DKI with a 3-T MR imager. Diffusion tensor tractography images of the anterior and posterior cingulum were generated. The mean kurtosis (MK) and conventional diffusion tensor parameters measured along the images in the anterior and posterior cingulum were compared between the groups. Receiver operating characteristic (ROC) analysis was also performed to compare the diagnostic abilities of the MK and conventional diffusion tensor parameters.Results
The MK and fractional anisotropy (FA) in the anterior cingulum were significantly lower in PD patients than in healthy controls. The area under the ROC curve was 0.912 for MK and 0.747 for FA in the anterior cingulum. MK in the anterior cingulum had the best diagnostic performance (mean cutoff, 0.967; sensitivity, 0.87; specificity, 0.94).Conclusions
DKI can detect alterations of the anterior cingulum in PD patients more sensitively than can conventional diffusion tensor imaging. Use of DKI can be expected to improve the ability to diagnose PD. 相似文献1000.
Chicken breast is not preferred in Japan because it is not juicy. In this study, the effect of combined high pressure and sodium hydrogen carbonate (NaHCO3) treatment on the texture and palatability of chicken breast was investigated. The sample used was broiler chicken breast. Meat samples were soaked in.0–.4 M NaHCO3 solution and then pressurized at 100–400 MPa. After pressurization, the samples were heated for 30 min at 80°C and cooled down in ice-cold water. High pressure and NaHCO3 treatment of broiler chicken breast resulted in increased water content, and decreased weight reduction and rupture stress. Moreover, meat exposed to 200 MPa pressurization and.3 M NaHCO3 treatment was judged tender, juicy and of good taste by sensory evaluation. The combination of high pressure and NaHCO3 treatment can be effectively used for broiler chicken breast production. 相似文献