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91.
Effect of the stoichiometry on the electronic structure of the Ni(111)/α-Al2O3(0001) interface: a first-principles investigation
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In this paper first-principles calculations of Ni(111)/α-Al2O3(0001) interfaces have been performed, and are compared with the preceding results of the Cu (111)/α-Al2O3(0001) interface [2004 Phil. Mag. Left. 84 425]. The AI- terminated and O-terminated interfaces have quite different adhesion mechanisms, which are similar to the Cu(111)/α Al2O3(0001) interface. For the O-terminated interface, the adhesion is caused by the strong O-2p/Ni-3d orbital hybridization and ionic interactions. On the other hand, the adhesion nature of the Al-terminated interface is the image-like electrostatic and Ni-Al hybridization interactions, the latter is substantial and cannot be neglected. Charge transfer occurs from Al2O3 to Ni, which is opposite to that in the O=terminated interface. The charge transfer direction for the Al-terminated and O-terminated Ni(111)/α-A1203(0001) interfaces is similar to that in the corresponding Cu(111)/α- Al2O3(0001) interface, but there exist the larger charge transfer quantity and consequent stronger adhesion nature, respectively. 相似文献
92.
Masanori Hino 《Potential Analysis》2002,16(3):249-264
For conservative symmetric diffusions on a general state space (X,m), the short time asymptotic behavior of tlog
X
1
A
T
t
1
B
dm is investigated, where T
t
is the associated semigroup and A and B are measurable subsets of X. It is proved that the superior limit is dominated by the inferior limit up to some absolute constant. When 2 of the associated Dirichlet form is lower bounded, it is shown that the limit exists for any A and B, and is described by the intrinsic metric between them. Applications to infinite-dimensional spaces and fractals are given. 相似文献
93.
Eguchi Y 《Biomedical chromatography : BMC》2002,16(8):500-503
Lipoprotein lipase (LPL) is a key enzyme which regulates the plasma triglyceride concentration by hydrolyzing triglycerides in chylomicrons and very-low-density lipoprotein (VLDL). The activity of LPL was conventionally analyzed using radio-labeled residues or direct sandwich-ELISA. An assay for lipoprotein lipase activity which used a nonradioactive substrate, tri-olein, is described. In this method, LPL activity was detected fluorometrically by reacting 9-anthryldiazomethane (ADAM) with the oleic acid generated from tri-olein by enzyme activity and separated by reversed-phase HPLC. This method has been optimized and the optimum enzyme incubation time and reaction time of the generated oleic acid with ADAM were both at 20 min. The method correlated well with the conventional method. 相似文献
94.
5-[4-(1-Hydroxyethyl)phenyl]-10,15,20-triphenylporphyrin (1a) and zinc porphyrin 1b were designed and synthesized to experimentally examine the validity of the transition-state model previously proposed for the lipase-catalyzed kinetic resolution of secondary alcohols. The lipases from Pseudomonas cepacia (lipase PS), Candida antarctica (CHIRAZYME L-2), Rhizomucor miehei (CHIRAZYME L-9), and Pseudomonas aeruginosa (lipase LIP) exhibited excellent enantioselectivity (E >100 at 30 degrees C). Subtilisin Carlsberg from Bacillus licheniformis (ChiroCLEC-BL) also showed high enantioselectivity for 1a (E = 140 at 30 degrees C), and the thermodynamic parameters were determined: DeltaDeltaH = -6.8 +/- 0.8 kcal mol(-1), DeltaDeltaS = -13 +/- 3 cal mol(-1) K(-1). Lipases and subtilisin showed R- and S-preference for 1, respectively. The mechanisms underlying the experimental observations are explained in terms of the transition-state models. The large secondary alcohol 1 is a powerful tool for investigating the conformation of the transition state of the enzyme-catalyzed reactions. The fact that 1 was resolved with high enantioselectivity strongly suggests that the gauche conformation, but not the anti conformation, is taken in the transition state, in agreement with the transition-state models involving the stereoelectronic effect. 相似文献
95.
[structure: see text] 8,11-Dideoxytetrodotoxin, an unnatural tetrodotoxin analogue, was synthesized in a highly stereoselective manner from a common intermediate in our synthetic studies on tetrodotoxin. The synthesis features neighboring group participation of trichloroacetamide for stereoselective hydroxylation, protection of ortho ester, and guanidine installation with Boc-protected isothiourea. 相似文献
96.
[reaction: see text] The stereoselectivity of nucleophilic addition of 2-trimethylsilyloxyfuran to N-gulosyl-C-alkoxymethylnitrones was investigated. It was found that the selectivity was highly dependent on the bulkiness of the C-substituent of the nitrone. The major adducts were elaborated into the key intermediate of polyoxin C. 相似文献
97.
Observation of the rest-atom layer of the Si(111)-(7 x 7) surface is performed by atomic force microscopy. By detecting the force due to the single chemical covalent bond formed between the tip and the sample surface, individual atoms on the layer were clearly resolved. Unprecedented high spatial resolution was achieved by setting the detection force at a small value and by reducing background forces due to the long-range interactions with the small oscillation amplitude of the cantilever and sharp probe tip. 相似文献
98.
Dannenmuller O Arakawa K Eguchi T Kakinuma K Blanc S Albrecht AM Schmutz M Nakatani Y Ourisson G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(4):645-654
Several biophysical properties of four synthetic archaeal phospholipids [one polyprenyl macrocyclic lipid A and three polyprenyl double-chain lipids (B, C, D) bearing zero, one or four double bonds in each chain] were studied using differential scanning calorimetry, electron and optical microscopies, stopped-flow/light scattering and solid-state 2H-NMR techniques. These phospholipids gave a variety of self-organized structures in water, in particular vesicles and tubules. These assemblies change in response to simple thermal convection. Some specific membrane properties of these archaeal phospholipids were observed: They are in a liquid-crystalline state over a wide temperature range; the dynamics of their polyprenyl chains is higher than that of n-acyl chains; the water permeability of the membranes is lower than that of n-acyl phospholipid membranes. It was also found that macrocyclization remarkably improves the barrier properties to water and the membrane stability. This may be related to the adaptation of Methanococcus jannaschii to the extreme conditions of the deep-sea hydrothermal vents. 相似文献
99.
An improved lattice action for gauge theories with Wilson fermions is presented. 相似文献
100.
Optical solitary waves that propagate in a Kerr medium exhibiting a power-law nonlocal response are studied analytically. The first-principles stability analysis based on quantum field theory shows that within the whole range of the exponent (the fractal dimension) the solitary wave can be stabilized. 相似文献