A probable hydrogen-bonded Meisenheimer complex: an unusually high S(N)Ar reactivity of nitroaniline derivatives with hydroxide ion in aqueous media

Observations show that nitroanilines exhibit an unusually high S(N)Ar reactivity with OH(-) in aqueous media in reactions that produce nitrophenols. S(N)Ar reaction of 4-nitroaniline (2a) in aqueous NaOH for 16 h yields 4-nitrophenol (4a) quantitatively, whereas a similar reaction of 4-nitrochlorobenzene (1a) gave 4a in 2% yield together with recovered 1a in 97%, suggesting that the leaving ability of the NH(2) group far surpasses that of Cl under these conditions. An essential feature of S(N)Ar reactions of nitroanilines is probably that the NH(2) leaving group participates in a hydrogen-bonding interaction with H(2)O. Density functional theory (DFT) calculations for a set of 4-nitroaniline, OH(-), and H(2)O suggest a possible formation of a Meisenheimer complex stabilized by hydrogen-bonding interactions and a six-membered ring structure. The results obtained here contrast with conventional S(N)Ar reactivity profiles in which nitroanilines are nearly unreactive with nucleophiles in organic solvents.     

Spectral Properties of the Linearization at the Burgers Vortex in the High Rotation Limit

We study a linearized operator of the equation for the axisymmetric Burgers vortex which gives a stationary solution to the three dimensional Navier–Stokes equations with an axisymmetric background straining flow. It is numerically known that the Burgers vortex obtains better stabilities as the circulation number (or the vortex Reynolds number) is increasing. Although the global stability of the axisymmetric Burgers vortex is already proved rigorously, mathematical understanding of this numerical observation has been lacking. In this paper we study a linearized operator that includes the circulation number as a parameter, and prove that if the operator is restricted on a suitable invariant subspace, then its spectrum moves to the left as the circulation number goes to infinity. As an application, we show that the axisymmetric Burgers vortex with a high rotation has a better stability, in the sense that the non-radially symmetric part of solutions to the associated evolution equation decays faster in time if the circulation number is sufficiently large.     

Prediction error criterion for selecting variables in a linear regression model

Several criteria, such as CV, C _p , AIC, CAIC, and MAIC, are used for selecting variables in linear regression models. It might be noted that C _p has been proposed as an estimator of the expected standardized prediction error, although the target risk function of CV might be regarded as the expected prediction error R _PE. On the other hand, the target risk function of AIC, CAIC, and MAIC is the expected log-predictive likelihood. In this paper, we propose a prediction error criterion, PE, which is an estimator of the expected prediction error R _PE. Consequently, it is also a competitor of CV. Results of this study show that PE is an unbiased estimator when the true model is contained in the full model. The property is shown without the assumption of normality. In fact, PE is demonstrated as more faithful for its risk function than CV. The prediction error criterion PE is extended to the multivariate case. Furthermore, using simulations, we examine some peculiarities of all these criteria.     

Enantioselective Protonation of Cyclic Carbonyl Ylides by Chiral Lewis Acid Assisted Alcohols

Chiral Lewis acid-catalyzed asymmetric alcohol addition reactions to cyclic carbonyl ylides generated from N-(α-diazocarbonyl)-2-oxazolidinones featuring a dual catalytic system are reported. Construction of a chiral quaternary heteroatom-substituted carbon center was accomplished in which the unique heterobicycles were obtained in good yields with high stereoselection. The alcohol adducts were successfully converted to optically active oxazolidine-2,4-diones by hydrolysis. Mechanistic studies by DFT calculations revealed that alcohols could be activated by Lewis acids, enabling enantioselective protonation of the carbonyl ylides.     

ANALYSIS OF PHOTOTRANSFORMATION INTERMEDIATES IN THE PATHWAY FROM THE RED-ABSORBING TO THE FAR-RED-ABSORBING FORM OF AVENA PHYTOCHROME BY A MULTICHANNEL TRANSIENT SPECTRUM ANALYZER

Phototransformation of the red-absorbing form of phytochrome (Pr) to the far-red-absorbing form (Pfr) was followed with a custom-built transient spectrum analyzer. Large phytochrome, which consisted of approximately 120000-dalton monomers, was immunopurified or conventionally purified from etiolated oat (Avena sativa L., cv. Garry) shoots. Phototransformation was initiated by exciting Pr with a 115-mJ, 600-ns half-width, 655-nm laser pulse. Absorption spectra were recorded on a microsecond time scale at predetermined times after the flash. It has been reported earlier that flash excitation of large oat Pr produces a transformation intermediate with maximum absorbance near 700 nm in a difference spectrum and that this intermediate decays by two kinetically distinct reactions. Difference spectra for these two reactions are indistinguishable. Both show bleaching centered at 690 nm with no detectable associated absorbance increase between 570 and 830 nm. Subsequent appearance of absorbance at 724 nm, which presumably but not necessarily represents the appearance of Pfr, had earlier been shown to occur by two kinetically distinct reactions for large oat phytochrome. Data presented here indicate in addition the occurrence of a third, slower reaction. Difference spectra for the two faster reactions are indistinguishable, both with maxima near 728 nm and minima near 650 nm. The difference spectrum for the slowest component, however, was qualitatively different exhibiting a maximum near 722 nm with no corresponding minimum. About 15-20% of the absorbance increase at 724 nm occurred by this slowest reaction, which exhibited a half-life of 3 s at 25°C and a Q₁₀ of 1.2 for immunopurified and 1.5 for conventionally purified phytochrome. The percentage occurring by this reaction was independent of temperature over the range studied (1-25dEC). For immunopurified phytochrome the enthalpy of activation, Gibbs free energy of activation, and entropy of activation of this slowest reaction were found to be about lOkJ-mol^-1, 75kJ.mol^-1, and -220 J.mol^-1 K^-1, respectively, and for conventionally purified phytochrome 25kJ.mol^-1, 75kJ.mol^-1and —170 J.mol^-1 K^-1, respectively. The thermodynamic characteristics of this reaction indicate that it may involve a significant ordering of the protein moiety as it transforms to Pfr.     

采用壳层效应屏蔽长度Monte Carlo方法计算溅射产额

使用ACAT模拟程序计算了不同离子碰撞在单原子材料上的溅射产额.采用山村等人提出的考虑壳层效应的理论屏蔽长度,原子间作用势用Moliére势.并将计算结果与实验数据和山村等的经验公式进行了比较.     

Nickel-catalyzed [3+1+1] cycloaddition reactions of alkenyl Fischer carbene complexes with methylenecyclopropanes

Methylenecyclopentanones were synthesized by the nickel-catalyzed [3+1+1] cycloaddition reactions of alkenyl Fischer carbene complexes with methylenecyclopropanes. The methylenecyclopropane was transformed into the C(2)-symmetric bis-cyclopentapyridazine derivative by reacting with p-toluenesulfonyl hydrazine.     

Velocity field after wave breaking

The velocity field in breaking water waves is considered in this paper. A numerical simulation describes in detail the transition from a primary overturning and consequent rebounding jets into a bore front, where the vorticity in the coherent large‐scale eddy structures devolves into turbulence. Spatial changes in the frequency spectra of the kinetic energy and the enstrophy are associated with the production, transport and dissipation of the Reynolds stress and the various wave and turbulent mixing length scales. Mean velocity fields and the wave and kinetic energy in a surf zone are evaluated. Fourier and wavelet spectral analysis is applied to study both the surface elevation and energy changes, and the distinction that must be made between spilling and plunging breakers is clarified in this paper. Copyright © 2002 John Wiley & Sons, Ltd.     

Temporal variation of electron density in a laser-perturbed discharge plasma and its relationship to the optogalvanic signal

By the method of microwave cavity resonance the authors have measured the temporal variation of the lctron density following the laser excitation of neon glow-discharge plasma, and the result is compared with the optogalvanic signal. It is found that the optogalvanic signal does not represent the change in the electron density; i.e., the time resolution is poor and the absolute magnitude is smaller by an order.