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101.
Yuki Yamamoto Jun‐ya Hasegawa Yoshikatsu Ito 《Journal of Physical Organic Chemistry》2012,25(3):239-247
The kinetics of carbamate formation from the reaction of carbon dioxide with α‐amino acids in D2O was first investigated by means of nuclear magnetic resonance spectroscopy. Potassium carbonate was used as the CO2 source. For each amino acid, the maximum carbamate yield, the apparent rate constant for the carbamate formation kapp, and the rate constants for the formation k1 and the breakdown k?1 of the carbamate were estimated. Plots of log k1 or log k?1 versus pKa of amino acids indicated that the formation rate k1 increased with the basicity (pKa) of amino acid, while the decomposition rate k?1 decreased. A Br?nsted β value of 0.39 was obtained from the former plot, being in good agreement with the previously reported ones (0.26–0.43). The observed negative pKa dependence of log k?1 (Br?nsted α = 0.34) is reasonable, because the carbamate decomposition is acid‐catalyzed and the steady‐state concentration of H+ should be higher for weaker basic amines. The charge (σ) and the lone‐pair energy (EN) at the nitrogen atom of the amino group were calculated. Although log k1 correlated with σ and EN, log k?1 was unrelated with both of these parameters. Considering that the carbamate formation (k1) is not only base‐catalyzed but should also be promoted by the nucleophilicity of the amino nitrogen, its correlation with σ and EN in addition to pKa is rational. The irrelevance of log k?1 to σ and EN is not surprising, because σ and EN are not a direct measure of [H+] of the solution. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
102.
Kazuaki Yoshimura Katsuhiko Okano Rumi Ishikawa Hidetoshi Yamamoto Michinori Sumimoto Kenji Hori 《Journal of Physical Organic Chemistry》2012,25(5):394-399
Synthesis yields of organic reactions are one of the most important factors in ranking synthesis routes created by synthesis route design systems such as Transform‐Oriented Synthesis Planning and Knowledge base‐Oriented Synthesis Planning. If it is possible to predict the yields of synthesis reactions before starting experiments, one can easily determine an order of synthesis routes for experimental works. In the present study, the reaction profiles of the Curtius rearrangement with different substituents were calculated to generate an equation predicting experimental yields of this reaction. Reactions followed by the formation of isocyanates were also analyzed to consider the relationship between reaction times and experimental yields. A partial least squares (PLS) regression was used to correlate the experimental yields with the calculated activation energies, Ea(calc), together with experimental conditions such as dielectric constants of solvents, reaction times, and reaction temperatures as explanatory variables. Although the PLS regression using all the data gave very poor results, we succeeded in making a model equation with R2 = 0.887 using a modified data set. However, there is a conflict between the predictability and the interpretability on the reaction time. This discrepancy mainly comes from unnecessarily long reaction times in the experiments for azides with calculated Ea values of less than 33 kcal mol–1. To construct a good model equation for the experimental yields of the Curtius reaction, we have to use data sets obtained from within 90 min of the reaction for the PLS regression. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
103.
The Heat Kernel on Hyperbolic Space 总被引:1,自引:0,他引:1
The purpose of this note is to provide a new proof for the explicitformulas of the heat kernel on hyperbolic space. By definition,the hyperbolic space Hn is a (unique) simply connected completen-dimensional Riemannian manifold with a constant negative sectionalcurvature 1. 1991 Mathematics Subject Classification58G32, 58G11. 相似文献
104.
We consider the approximate controllability by interior control of a partial differential equation with time derivatives of non-integer order. First, we prove the well-posedness of the inhomogeneous problem for the controlled system. Next, we study the dual system and show a weak type of unique continuation property. Finally, we prove the approximate controllability. 相似文献
105.
We derive some rigorous results on the chiral phase transition in QCD and QCD-like theories with a large number of colors, N(c), based on the QCD inequalities and the large-N(c) orbifold equivalence. We show that critical phenomena and associated soft modes are forbidden in flavor-symmetric QCD at finite temperature T and finite but not so large quark chemical potential μ for any nonzero quark mass. In particular, the critical point in QCD at a finite baryon chemical potential μ(B)=N(c)μ is ruled out, if the coordinate (T, μ) is outside the pion condensed phase in the corresponding phase diagram of QCD at a finite isospin chemical potential μ(I)=2μ. 相似文献
106.
Shigehiro Hirano Ko-Ichi Yamamoto Hiroshi Inui Ming Ji Min Zhang 《Macromolecular Symposia》1996,105(1):149-154
The following dry composite beads (diameter 1.0-1-2 mm) were prepared: chitin-CaCO3, chitosan-CaCl2. chitosan-CuCl2, partially N-acetylated chitosan-CuCl2, chitosan-CuSO4, chitosan-Fe3O4, chitin-SiO2. Each of chitosan-CuCl2, chitosan-CuSO4 and chitin-CaCl2 composite beads was treated in aqueous K2CO3 at room temperature to afford a mixture of metal carbonates and hydroxides on chitin or chitosan chain. 相似文献
107.
Six reducing monosaccharides (mannose, galactose, fucose, glucose, xylose, and arabinose) were derivatized with 1-phenyl-3-methyl-5-pyrazolone (PMP) and chiral resolution of these racemic PMP-monosaccharides was studied by ligand-exchange CE using borate anion as a central ion of the chiral selector and (S)-3-amino-1,2-propanediol (SAP) as a chiral selector ligand. PMP-mannose, PMP-galactose and PMP-fucose were successfully enantioseparated. Lowering the capillary temperature increased the resolution of PMP-mannose system, but decreased that of PMP-galactose and PMP-fucose systems. Whereas the maximum resolution was obtained at pH 8.9 in the PMP-mannose system, resolution increased gradually with pH in the PMP-galactose and PMP-fucose systems. Expecting the formation of the ternary borate complexes with SAP and PMP-monosaccharide in the CE experiments, the optimized structures of the borate diastereomers were obtained by semiempirical molecular orbital calculations to discuss the structural difference of the diastereomers in connection with the enantioseparation behaviors. 相似文献
108.
The utility of the new class of chiral ligand, tethered bis(8-quinolinol) (TBOxH), is further explored. Its chromium complex, TBOxCr(III)Cl, effectively catalyzes the Nozaki-Hiyama allylation reactions of various aldehydes at room temperature with high yield (up to 95%) and high enantioselectivity (up to 99% ee). The scope of the present method is shown to be wide, and this method represents an efficient access to chiral homoallylic alcohols. 相似文献
109.
110.
Enders D Nagao T Nakayama T Aono M 《Langmuir : the ACS journal of surfaces and colloids》2007,23(11):6119-6125
The adsorption and desorption of Au nanoparticles (AuNP) in colloidal D2O suspension on the (3-aminopropyl)triethoxysilane treated SiO2/Si surface was investigated by in situ attenuated total reflection surface enhanced infrared absorption (ATR-SEIRA) spectroscopy with a liquid flow cell. With increasing surface density of AuNP, the absorption of the vibrational modes of D2O and of the citrate molecules covering the AuNP increases due to SEIRA. Repulsive electrostatic Coulomb forces between the AuNP lead to the saturation of the AuNP surface density at submonolayer coverage. We show that the adsorption kinetics can be investigated by monitoring in situ the molecular vibrational modes of D2O and the citrate molecules. Furthermore, we clarify that the adsorption process can be described very well by a diffusion-limited first-order Langmuir kinetics model. When exposing a saturated AuNP submonolayer to 2-aminoethanethiol (AET)/D2O solution, the AuNP are removed from the surface and the IR absorption of the D2O vibrational modes become weaker again. Taking into account the time dependencies of the OD and the CH peaks, we propose a microscopic model where the AET molecules quickly adsorb on the AuNP by replacing most of the precovering citrate molecules exposed to the AET solution. As this takes place, the AuNP agglomerate-as we could detect with scanning electron microscopy-and are finally removed from the surface. 相似文献