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111.
The reaction of an α-haloketone with a nucleophile has three reaction channels: carbonyl addition, direct substitution, and proton abstraction. DFT calculations for the reaction of PhCOCH(2)Br with OH(-) showed that there exists an addition/substitution TS on the potential energy surface, in which OH(-) interacts with both the α- and carbonyl carbons. The intrinsic reaction coordinate calculations revealed that the TS serves as the TS for direct substitution for XC(6)H(4)COCH(2)Br with an electron-donating X or a X less electron-withdrawing than m-Cl, whereas the TS serves as the TS for carbonyl addition for derivatives with a X more electron-withdrawing than m-CF(3). Trajectory calculations starting at respective TS indicated that the single TS can serve for the two mechanisms, substitution and addition, through path bifurcation after the TS for borderline substrates. The reaction is the first example of dynamic path bifurcation for fundamental reaction types of carbonyl addition and substitution. 相似文献
112.
Nobuyoshi Takahashi 《代数通讯》2013,41(3):971-988
For varieties over a field k, we define motivic measures with values in ordered fields, using point counting over finite fields and taking the limits with respect to ultrafilters. Some properties and problems related to such measures are discussed. We define similar measures for algebraic dynamical systems by counting periodic points, and explain how they can be used to prove certain statements, such as the non-rationality of a motivic zeta function. 相似文献
113.
Tatsuo Kimura Dr. Nobuyoshi Miyamoto Dr. Xiangju Meng Dr. Tatsuki Ohji Dr. Kazumi Kato Dr. 《化学:亚洲杂志》2009,4(9):1486-1493
Hierarchically porous titania films were fabricated by dual templating using a triblock copolymer such as Pluronic F127 and polystyrene (PS) beads, affording mesoporous films with controlled macroporosity. The presence of the triblock copolymer in the precursor solutions suppressed a regular accumulation of spherical PS beads, and PS‐derived macropores could be dispersed over the whole mesoporous titania film through rapid fabrication by spin‐coating. Some of the macropores were clustered, but the presence of the large spaces was important for keeping the mesostructure after calcination. Photodegradation of methylene blue (MB) was investigated by using the photoactive anatase films. The photodegradation of MB over the porous anatase films was accelerated by effective diffusion of MB molecules in the PS‐derived macropores, but it was important for improving photocatalytic performance to regulate the balance between the effectiveness of the diffusion in the macropores and the decrease of the surface area from the embedded macropores, as well as the reduction in the transparency of the porous films. 相似文献
114.
In a three-step sequence starting from readily available starting materials, 2,3-carbon disubstituted furo[2,3-b]pyridines can be accessed in good yields and purity. Furo[2,3-b]pyridines bearing ester, amide and ketone groups at the 2-position can be prepared with a variety of aryl and alkyl groups at the 3-position. 相似文献
115.
Miyamoto N Yamamoto H Kaito R Kuroda K 《Chemical communications (Cambridge, England)》2002,(20):2378-2379
Exfoliated K4Nb6O17 bilayer nanosheets in extraordinarily large size (ca. 100 microns) were prepared by the direct reaction of K4Nb6O17.3H2O crystals with an aqueous solution of propylamine; the size was extremely larger than that of exfoliated nanosheets (several microns) reported previously. 相似文献
116.
An oxorhenium(V) dimer, [PMeReO(mtp)](2), D, where mtpH(2) is 2-(mercaptomethyl)thiophenol, catalyzes oxygen atom transfer reaction from methyl phenyl sulfoxide to triarylphosphines. Kinetic studies in benzene-d(6) at 23 degrees C indicate that the reaction takes place through the formation of an adduct between D and sulfoxide. The equilibrium constants, K(DL), for adduct formation were determined by spectrophotometric titration, and the values of K(DL) for MeS(O)C(6)H(4)-4-R were obtained as 14.1(2), 5.7(1), and 2.1(1) for R = Me, H, and Br, respectively. Following sulfoxide binding, oxygen atom transfer occurs with either internal or external nucleophilic assistance. Because [MeReO(mtp)](2) is a much more reactive catalyst than its monomerized form, MeReO(mtp)PPh(3), loss of the active catalyst during the time course of the reaction must be taken into account as a part of the kinetic analysis. As it happens, sulfoxide catalyzes monomerization. Monomerization by triarylphosphines was also studied in the presence of sulfoxide, and a mechanism for that reaction was also proposed. Both the phosphine-assisted monomerization and the phosphine-assisted pathway for oxygen atom transfer involve transition states with ternary components, D, sulfoxide, and phosphine, which we suggest are structural isomers of one another. 相似文献
117.
Let B be a line or a smooth conic in 2. We give a recursive formula for certain linear combinations of the genus 0 relative Gromov-Witten invariants of (2,B). After change of sign, this is equivalent to the WDVV equation for the equivariant local Gromov-Witten invariants of 2 in ᵊA(–B). We show that these invariants coincide up to sign.
Mathematics Subject Classification (2000):14N35, 14N10 相似文献
118.
It is shown that, in order for the U(1) Goldstone boson to decouple from the physical sector, a third rank skew-symmetric tensor gauge field theory has to be realized dynamically by asymptotic fields of bound states in QCD. The abelian-like gauge invariance of this tensor gauge theory is just a realization of the original QCD gauge (BRS) invariance which hence assures the decoupling of all the bound-state modes by the “quarlet mechanism”. A general procedure for fixing gauges in such types of skew-symmetric tensor gauge theories is also presented. 相似文献
119.
A new polymorph of FeAlO3 at high pressure 总被引:1,自引:0,他引:1
Nagai T Hamane D Devi PS Miyajima N Yagi T Yamanaka T Fujino K 《The journal of physical chemistry. B》2005,109(39):18226-18229
Synchrotron X-ray diffraction measurements confirmed that a new polymorph of FeAlO3 could be synthesized at about 1800 K and 72 GPa. This phase can be indexed on an orthorhombic cell and transforms into the trigonal form on release of pressure. The c/a ratio of about 2.71 of the trigonal phase suggests corundum structure of FeAlO3 rather than LiNbO3 or ilmenite structure. This conclusion also suggests that the high-pressure orthorhombic phase could be the Rh2O3(II) structure rather than the GdFeO3-type perovskite structure. 相似文献
120.