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11.
D abstraction (ABS) by H at Ru(0 0 1) surfaces initially saturated with D adatoms has been investigated using in situ mass spectrometry. HD and D2 desorption rates are measured at various surface temperatures T as a function of H exposure time. Yield of D2 desorption increases with T, while that of HD is little affected. Analyzing the measured rate curves, HD and D2 desorption orders are evaluated to be 1.7 ± 0.1 and 2.5 ± 0.1, respectively, with respect to D coverage θD. To pursue the origin of the derived non-integral reaction orders the rate curves are further analyzed with the rate equations constructed to involve several ABS channels. Consequently, we find that the HD desorption is mainly governed by a second-order rate law in θD rather than the conventional hot atom-mediated ABS reaction even when it is corrected to include an isotope effect on ABS. We argue that such second-order ABS kinetics becomes important when the H atoms in excited state of chemisorption have energetically relaxed to some extent, and thereby tend to reside at, e.g. hexagonal closed packed hollow sites, interacting with nearby adatoms. On the other hand, the D2 rate curves can be fit with third-order kinetics, consistent with the Langmuir-Hinshelwood mechanism in a super-saturation state. The isotope effect plays an essential role in the ABS reaction of D abstraction by H which competes with H abstraction by H as D adatoms are replaced by H atoms. 相似文献
12.
Thomas T. Nakashima Kristopher J. Harris Roderick E. Wasylishen 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2010,202(2):162-172
For quadrupolar nuclei with spin quantum numbers equal to 3/2, 5/2 and 7/2, the intensities of the NMR transitions in a single crystal are examined as a function of the rf excitation flip angle. Single-quantum NMR intensities are calculated using density matrix theory beginning under various non-equilibrium conditions and are compared with those determined experimentally. As a representative spin-3/2 system, the flip-angle dependence of the 23Na NMR intensities of a single crystal of NaNO3 was investigated beginning with the inversion of the populations associated with one of the satellite transitions. Subsequently, the populations of both satellite transitions were inverted using highly frequency-selective hyperbolic secant pulses. Calculated and experimental intensities are in good agreement. As an example of a spin-5/2 system, the flip-angle dependence of the 27Al NMR transition intensities was determined using a single crystal of sapphire, Al2O3, starting under different nuclear spin population conditions. The experimental trends mimicked those predicted by the density matrix calculations but the agreement was not as good as for the spin-3/2 case. Some SIMPSON simulations were also carried out to confirm the results generated by our density matrix calculations. The theoretical flip-angle behavior of the NMR transition intensities obtained from a spin-7/2 spin system is also discussed. 相似文献
13.
Fe(NCS)2(bpa)2, Co(NCS)2(bpa)2, and Fe0.5Co0.5(NCS)2(bpa)2 were synthesized. X-ray structural analysis revealed that the structure was the same among the three complexes. Although the metal-ligand distance in the mixed crystals was shorter than the distance in Fe(NCS)2(bpa)2 and was similar to that in Co(NCS)2(bpa)2, the spin state remained temperature-independent FeII high-spin state in 57Fe M?ssbauer spectra. 相似文献
14.
Spectroscopic and thermodynamic investigations on complexation of naphthalene-appended amino-beta-cyclodextrins 1 and 2 with cyclic alcohols (cyclohexanol and cycloheptanol) and acyclic alcohols (1-pentanol, 2-pentanol, 1-hexanol, and 1-heptanol) have been carried out. Host 1 exhibits a drastic fluorescent enhanced-signal change in the presence of alcohol guests in aqueous solution. [structure: see text] 相似文献
15.
Moriyuki Sato Miyuki Notsu Shinji Nakashima Yuko Uemoto 《Macromolecular rapid communications》2001,22(9):681-686
New semi‐rigid thermotropic liquid crystalline (LC) polyesters composed of a quaterphenyl analogue of 2,2′‐bis(1,3,4‐thiadiazole) were synthesized by high‐temperature solution polycondensation of a dioxydiundecanol derivative of 5,5′‐diphenyl‐2,2′‐bis(1,3,4‐thiadiazole) with four diacyl chlorides, whose structures were characterized by FT‐IR and 13C NMR spectroscopy, as well as elemental analysis. Differential scanning calorimetry (DSC) measurements and texture observations using polarizing microscopy displayed that all the polyesters form stable enantiotropic smectic and/or nematic LC phases. Solution and solid state absorption and fluorescence spectra indicated that the polyesters show absorption maxima arising from the 2,2′‐bis(1,3,4‐thiadiazole) moiety and emit bluish green light, the Stokes shifts being 129 nm in solution and 60–64 nm in the solid state. Band gap energies of the polyesters calculated from the solid state absorption spectra were 2.67–2.82 eV. 相似文献
16.
Norio Kitadai Tadashi Yokoyama Satoru Nakashima 《Journal of colloid and interface science》2009,338(2):395-401
The adsorption behavior of lysine on montmorillonite in aqueous solution was investigated by in situ attenuated total reflectance infrared (ATR-IR) spectroscopy. To distinguish the protonation states of α-amino group, side-chain amino group and carboxyl group in lysine structure using ATR-IR spectra (i.e., NH2 versus and COO− versus COOH), pH-induced spectral changes of dissolved lysine were firstly measured and correlated with the thermodynamically calculated dissociation states of lysine (di-cationic, cationic, zwitterionic and anionic states). The obtained result was applied to interpret the ATR-IR spectra of lysine adsorbed on montmorillonite. We found that the adsorbed lysine was dominantly present as cationic state over the whole range of tested pH (pH = 4.9–9.7). This indicates that the adsorption is mainly driven by electrostatic interaction between the negatively charged montmorillonite surface and positively charged cationic lysine. We also found that lysine interacts with montmorillonite surface through the protonated side-chain amino group. This result suggests that lysine has a preferred vertical orientation, with the side-chain amino group pointing toward the surface. 相似文献
17.
Three new spiculoic acids 1-3 and two members of a new closely related family of natural products named zyggomphic acids 4 and 5 were isolated from the very little studied marine sponge Plakortis zyggompha. Both families of compounds share a unique trans-hydrindan-2-one skeleton with six stereogenic centers. A total of 15 new metabolites were isolated from this sponge, all are of polyketide origin. The structures were elucidated using LC-MS, 1D, and 2D NMR methods. The absolute stereochemistry was determined by circular dichroism. The large number of close bioactive analogues allowed us to propose preliminary structure-activity relationships as antitumoral and antimycobaterial agents. 相似文献
18.
The transition temperatures between high- and low-spin states of the assembled spin-crossover complexes, Fe(NCX)2(bpa)2(guest) (X = S, Se, BH3; bpa = 1,2-bis(4-pyridyl)ethane; guest = biphenyl, 2-nitrobiphenyl, diphenylmethane, or 1,4-dichlorobenzene), were compared with the Mössbauer parameters. The transition temperature increases when the QS value of FeII high-spin state becomes small. The transition temperature also increases by changing the anion from NCS to NCSe and then to NCBH3. 相似文献
19.
Road signs must provide a conspicuous signal to a wide variety of drivers over a broad range of environmental and geometric
conditions. Recently, there are an increasing number of applications in which light emitting diodes (LEDs) are used as the
light source, including critical transportation signaling. In the presence of fog, the resulting visual signal is disturbed
due to light scattering by airborne water droplets. By measuring LED brightness with human spectral sensitivity in various
densities and various droplet sizes (10, 30, 50, and 100 μm), it is understood that the particle size distribution (fog droplet
size) and density of fog does affect visibility in fog. The colored LEDs that contain a yellow component had high brightness
evaluation, blue component had low brightness evaluation in all densities and different droplet sizes. The result in this
paper can contribute to air and land traffic safety and the prevention of accidents. 相似文献
20.
Kon N Takemura H Otsuka K Tanoue K Nakashima S Yasutake M Tani K Kimoto J Shinmyozu T Inazu T 《The Journal of organic chemistry》2000,65(12):3708-3715
Macropolycyclic cage compounds were synthesized by a direct reaction between diamines and bis(bromomethyl) compounds. The procedure for constructing the polycyclic cage structure is simple and straightforward. The macropolycyclic compounds obtainable from this cyclization procedure are three-dimensional cage compounds, and any other isomers were not obtained except for two examples. Benzene, pyridine, and aliphatic units could be introduced into the cage structure. The macrocycles that have strong cation affinity were obtained as their potassium complexes. 相似文献