Pathwise Uniqueness and Non-explosion Property of Skorohod SDEs with a Class of Non-Lipschitz Coefficients and Non-smooth Domains

Journal of Theoretical Probability - Here, we study stochastic differential equations with a reflecting boundary condition. We provide sufficient conditions for pathwise uniqueness and...     

Analysis of variance for high-dimensional time series

Analysis of variance (ANOVA) is tailored for independent observations. Recently, there has been considerable demand for ANOVA of high-dimensional and dependent observations in many fields. For example, it is important to analyze differences among industry averages of financial data. However, ANOVA for these types of observations has been inadequately developed. In this paper, we thus present a study of ANOVA for high-dimensional and dependent observations. Specifically, we present the asymptotics of classical test statistics proposed for independent observations and provide a sufficient condition for them to be asymptotically normal. Numerical examples for simulated and radioactive data are presented as applications of these results.     

Synthesis,Structure, and Chiroptical Properties of Indolo- and Pyridopyrrolo-Carbazole-Based C2-Symmetric Azahelicenes

Treatment of 11,12-bis(1,1’-biphenyl-3-yl or 6-phenylpyridin-2-yl)-substituted 11,12-dihydro-indolo[2,3-a]carbazole with an oxidizing system of Pd(II)/Ag(I) induced effective double dehydrogenative cyclization to afford the corresponding π-extended azahelicenes. The optical resolutions were readily achieved by a preparative chiral HPLC. It was found that the pyridopyrrolo-carbazole-based azahelicene that contains four nitrogen atoms exhibits ca. 6 times larger dissymmetry factors both in circularly dichroism (CD) and circularly polarized luminescence (CPL), |g_CD| and |g_CPL| values being 1.1×10⁻² and 4.4×10⁻³, respectively, as compared with the parent indolocarbazole-based azahelicene. Theoretical calculations at the RI-CC2 level were employed to rationalize the observed enhanced chiroptical responses. The (chir)optical properties of the former helicene was further tuned by a protonation leading to remarkable red-shift with a considerable enhancement of the |g_CPL| value.     

Asymmetric Synthesis of Axially Chiral Anilides by Enantiotopic Lithiation of Tricarbonyl(N-methyl-N-acyl-2,6-dimethylanilide)chromium Complex

Axially chiral N-methylanilides were synthesized by enantioselective lithiation of prochiral tricarbonyl(N-methyl-N-pivaloyl-2,6-dimethylaniline)chromium (1) with the lithium amide of the 4-methylpiperazinylethylamine derivative 13 followed by electrophilic quenching up to 97% ee in good yields. The resulting axially chiral chromium-complexd anilides 2 were oxidized under air to give the axially chiral anilides 14 in enantiomerically active form without axial bond rotation at room temperature.     

Electrical detection of single methylcytosines in a DNA oligomer

We report label-free electrical detections of chemically modified nucleobases in a DNA using a nucleotide-sized electrode gap. We found that methyl substitution contributes to increase the tunneling conductance of deoxycytidines, which was attributed to a shift of the highest occupied molecular orbital level closer to the electrode Fermi level by methylation. We also demonstrate statistical identifications of methylcytosines in an oligonucleotide by tunneling current. This result suggests a possible use of the transverse electron-transport method for a methylation level analysis.     

Silica gel promotes reductions of aldehydes and ketones by N-heterocyclic carbene boranes

N-Heterocyclic carbene boranes (NHC-boranes) such as 1,3-dimethylimidazol-2-ylidine trihydridoborane (diMe-Imd-BH(3)) serve as practical hydride donors for the reduction of aldehydes and ketones in the presence of silica gel. Primary and secondary alcohols are formed in good yields under ambient conditions. Aldehydes are selectively reduced in the presence of ketones. One, two, or even all three of the boron hydrides can be transferred. The process is attractive because all the components are stable and easy to handle and because both the reaction and isolation procedures are convenient.     

Chirality effects on core-periphery connection in a star-burst type tetranuclear Ru(III) complex: application of vibrational circular dichroism spectroscopy

Vibrational circular dichroism (VCD) spectroscopy was applied to study the stereochemical properties of a star-burst type tetranuclear Ru(III) complex, Δ-(or Λ-)[{Δ-(or Λ-)-Ru(III)(acac)(2)(taet)}(3)Ru(III)] (acac = acetylacetonato; taet = tetraacetylethanato). By comparing the VCD spectra of eight diastereomeric enantiomers, it was shown that the spectra reflected the homo- or hetero-chiral nature of the bridging part connecting the central core and the peripheral region.     

Electrophilic addition to o-ArY-substituted phenylalkynes. A highly selective cyclization controlled by heteroatoms

Treatment of -(phenyloxy)phenylalkyne with HClO₄ or HBF₄ gave dibenz(b, f)oxepin , whereas the sulfur analogue, -(phenylthio)phenylalkyne , provided 1-phenyl-1-benzothiophenium salts .     

Asymptotic theory of parameter estimation by a contrast function based on interpolation error

Interpolation is an important issue for a variety fields of statistics (e.g., missing data analysis). In time series analysis, the best interpolator for missing points problem has been investigated in several ways. In this paper, the asymptotics of a contrast function estimator defined by pseudo interpolation error for stationary process are investigated. We estimate parameters of the process by minimizing the pseudo interpolation error written in terms of a fitted parametric spectral density and the periodogram based on observed stretch. The estimator has the consistency and asymptotical normality. Although the criterion for the interpolation problem is known as the best in the sense of smallest mean square error for past and future extrapolation, it is shown that the estimator is asymptotically inefficient in general parameter estimation, which leads to an unexpected result.     

Structural Characteristic of Folding/Unfolding Intermediate of Pokeweed Anti-viral Protein Revealed by Time-resolved Fluorescence

The structural feature of unfolding intermediate of pokeweed anti-viral protein (PAP) was characterized using time-resolved fluorescence spectroscopic methods to elucidate protein folding/unfolding process. CD and fluorescence spectra consistently demonstrated that the unfolding of PAP completed at 4 M of guanidine hydrochloride (GuHCl). The fluorescence resonance energy transfer (FRET) and time-resolve fluorescence depolarization analysis of Trp208 and Trp237 located in the C-terminal domain of PAP suggested that peculiar unfolding intermediate populated before reaching to the unfolding state. The FRET distance of Trp237 to Tyr182 was extended to more than 28 Å with keeping the compact conformation in the unfolding intermediate state populated in the presence of 2 M GuHCl. On the other hand, Trp208 maintained the energy transfer pair with Tyr72 near the active site, although the rotational freedom was increased a little. There results suggest that the most distinguished structural feature of the unfolding intermediate of PAP is the separation of C-terminal domain from N-terminal domain. FRET and fluorescence depolarization studies also showed that C-terminal domain would be more separated to liberate the segmental motions of Trp208 and Trp237 distinctly at the unfolding state.