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101.
Suzumura J Hosoya N Nagao S Mitsui M Nakajima A 《The Journal of chemical physics》2004,121(6):2649-2654
We have studied the electronic structures of several gas phase exohedral lanthanide (Ln)-C(60) clusters, Ln(n)C(60) (Ln=Pr, Ho, Tb, Tm, Eu, and Yb) with n=1-4, by photoionization spectroscopy of the neutrals and photoelectron spectroscopy of their anions. Both of the spectroscopic analyses reveal that most of the Ln atoms preferably take +3 oxidation states, while Eu atoms alone assume +2 oxidation states, and that C(60) accepts up to twelve donated electrons in Ln(n)C(60). An additional photoionization examination of the oxygen atom mixing into the Ln(n)C(60) clusters demonstrated that each oxygen atom reduces two electrons from C(60). This result implies that the number of accepted electrons in C(60) can be varied by a suitable choice of the number of Ln atoms and O atoms. 相似文献
102.
Ogata Atsushi Mizuno Koichi Kushiyama Satoshi Yamamoto Toshiaki 《Plasma Chemistry and Plasma Processing》1998,18(3):363-373
The behavior of lattice oxygen species of the ferroelectric material during methane oxidation was investigated using a nonthermal plasma reactor packed with BaTiO
3
pellets. Lattice oxygen species in BaTiO
3
play an important role in the formation of N
2
O and the oxidation of CH
4
. The oxidation products such as CO and CO
2
were formed from independent reaction pathways. Lattice oxygen species were able to preferentially oxidize the carbon species deposited on the pellet surface into CO. Also, N
2
O and NO
x
were independently formed in the N
2–O
2
reaction, suggesting that different oxygen species give N
2
O and NO
x. N
2
O was produced by the oxidation of molecular nitrogen with lattice oxygen species. 相似文献
103.
Some localized singlet 1,3-σ-diradicals, C(MH2)3C, (M = Si, Ge, Sn, Pb) were theoretically designed by the orbital phase theory and density functional theory calculations. The bicyclic carbon-centered singlet diradicals were more stable than the lowest triplets. Except for M = C, σ-bonded isomers were not located for 1,3-σ-diradicals. 1,4-σ-diradicals, C(M2H4)3C, also had singlet ground states, but they were less stable than σ-bonded isomers. 相似文献
104.
Bis-crown ethers in which the benzo-15-crown-5 units were linked to 1,1′-positions of metallocene (M = Fe or Ru) with amide, ester, or ? C? C? bonds were synthesized. Complexing ability of the compounds with alkali, alkali earth, and transition metal cations were measured by the solvent extraction method. The results showed that these crown ethers had high affinity toward alkali metal cations (Li+, Na+, K+, and Rb+) and heavy-metal cations (Ag+ and Tl+). The difference of complexing ability for metal cations between ferrocene and ruthenocene derivatives could not be detected significantly. The extractability of metallocene-bis-crown ethers for metal cations was more larger than that of the corresponding mono-crown ethers, and irregular increments of extractability were explained by assuming the existence of a mixture of 1:1 and 2:1 complexes. 相似文献
105.
Kudoh T Fukuoka M Ichikawa S Murayama T Ogawa Y Hashii M Higashida H Kunerth S Weber K Guse AH Potter BV Matsuda A Shuto S 《Journal of the American Chemical Society》2005,127(24):8846-8855
We previously developed cyclic ADP-carbocyclic ribose (cADPcR, 2) as a stable mimic of cyclic ADP-ribose (cADPR, 1), a Ca(2+)-mobilizing second messenger. A series of the N1-ribose modified cADPcR analogues, designed as novel stable mimics of cADPR, which were the 2"-deoxy analogue 3, the 3"-deoxy analogue 4, the 3"-deoxy-2"-O-(methoxymethyl) analogue 5, the 3"-O-methyl analogue 6, the 2",3"-dideoxy analogue 7, and the 2",3"-dideoxydidehydro analogue 8, were successfully synthesized using the key intramolecular condensation reaction with phenylthiophosphate-type substrates. We investigated the conformations of these analogues and of cADPR and found that steric repulsion between both the adenine and N9-ribose moieties and between the adenine and N1-ribose moieties was a determinant of the conformation. The Ca(2+)-mobilizing effects were evaluated systematically using three different biological systems, i.e., sea urchin eggs, NG108-15 neuronal cells, and Jurkat T-lymphocytes. The relative potency of Ca(2+)-mobilization by these cADPR analogues varies depending on the cell-type used: e.g., 3"-deoxy-cADPcR (4) > cADPcR (2) > cADPR (1) in sea urchin eggs; cADPR (1) > cADPcR (2) approximately 3"-deoxy-cADPcR (4) in T-cells; and cADPcR (2) > cADPR (1) > 3"-deoxy-cADPcR (4) in neuronal cells, respectively. These indicated that the target proteins and/or the mechanism of action of cADPR in sea urchin eggs, T-cells, and neuronal cells are different. Thus, this study represents an entry to cell-type selective cADPR analogues, which can be used as biological tools and/or novel drug leads. 相似文献
106.
Tatsuhiko Kashimura Tomoya Ikezaki Yusuke Ohta Satoshi Yabushita 《Journal of computational chemistry》2019,40(2):482-499
One of the most spectacular yet unsolved problems for the ICN -band photodissociation is the non-statistical spin-rotation F1 = N + 1/2 and F2 = N − 1/2 populations for each rotation level N of the CN fragment. The F1/F2 population difference function f(N) exhibits strong N and λ dependences with an oscillatory behavior. Such details were found to critically depend on the number of open-channel product states, namely, whether both I (2P3/2) and I (2P1/2) are energetically available or not as the dissociation partner. First, in the asymptotic region, the exchange and dipole-quadrupole inter-fragment interactions were studied in detail. Then, as the diabatic basis, we took the appropriate symmetry adapted products of the electronic and rotational wavefunctions for the F1 and F2 levels at the dissociation limits. We found that the adiabatic Hamiltonian exhibits Rosen–Zener–Demkov type nonadiabatic transitions reflecting the switch between the exchange interaction and the small but finite spin-rotation interaction within CN at the asymptotic region. This non-crossing type nonadiabatic transition occurs with the probability 1/2, that is, at the diabatic limit through a sudden switch of the quantization axis for CN spin S from the dissociation axis to the CN rotation axis N . We have derived semiclassical formulae for f(N) and the orientation parameters with a two-state model including the 3A′ and 4A′ electronic states, and with a four-state model including the 3A′ through 6A′ electronic states. These two kinds of interfering models explain general features of the F1 and F2 level populations observed by Zare's group and Hall's group, respectively. © 2018 Wiley Periodicals, Inc. 相似文献
107.
Vallée RA Marsal P Braeken E Habuchi S De Schryver FC Van der Auweraer M Beljonne D Hofkens J 《Journal of the American Chemical Society》2005,127(34):12011-12020
Experimental (Single Molecule Spectroscopy) and theoretical (quantum-chemical calculations and Monte Carlo and molecular dynamics simulations) techniques are combined to investigate the behavior and dynamics of a polymer-dye molecule system. It is shown that the dye molecule of interest (1,1'-dioctadecyl-3,3,3',3'-tetramethylindo-dicarbocyanine) adopts two classes of conformations, namely planar and nonplanar ones, when embedded in a poly(styrene) matrix. From an in-depth analysis of the fluorescence lifetime trajectories, the planar conformers can be further classified according to the way their alkyl side chains interact with the surrounding poly(styrene) chains. 相似文献
108.
The reaction potential map (RPM) method has been extended so that the molecular reactivity towards nucleophiles can be analyzed. An anion consisting of the nucleus with + 1 charge and a pair of electrons was adopted as the model nucleophile. From the interaction energy between a substrate and this model particle, RPM and its component maps were obtained. With respect to practical applications, the reactivities of acrylic acid and acrylonitrile towards nucleophiles were examined. In these molecules, the exchange interaction as well as the charge-transfer interaction were found to be very important in the elucidation of the observed site selectivity. 相似文献
109.
Kiyoshi Hasebe Satoshi Hikima Hitoshi Yoshida 《Fresenius' Journal of Analytical Chemistry》1991,339(4):261-263
Summary The covalent bonding of l-lactate oxidase (no E.C.) to cross-linked copolymers of chitosan (Chitopearl) using the glutaraldehyde method is described and applied to the determination of l-lactate in serums of diseased and normal animals. The bioreactor packing of the immobilized enzyme is stable for at least 4 months and can be continuously used for the rapid and simple determination of l-lactate. The reduction current of pyruvate, corresponding to the product of enzymatic reaction, is determined by differential pulse polarography. The reproducibility (RSD) for 10 mol/l l-lactate is 0.78% (n=6) and the detection limit is 0.62 mol/l (k=2, confidence level 97.72%). 相似文献
110.
Minoru Tanaka Masanobu Yoshinaga Satoshi Asano Yuko Yamashoji Yoshihiro Kawaguchi 《Fresenius' Journal of Analytical Chemistry》1992,343(12):896-900
Summary The enantiomeric separation ability of unmodified and methylated cyclodextrins (CDs) during capillary zone electrophoresis (CZE) was investigated using twelve dansylamino acids. Unmodified - and -CDs exhibited high enantioselectivities. -CD could scarcely separate the enantiomers before and after dimethylation, but obtained enantioselectivity after trimethylation. On the other hand, dimethylation of -CD removed much of its high enantioselectivity. Moreover, the chemical modifications produced a reverse in the migration order of the enantiomers. The inclusion of dansyl-DL-phenylalanine with CDs was evaluated using 600 MHz 1H NMR spectroscopy. 相似文献