Remote asymmetric induction with vinylketene silyl n,o-acetal

A highly regio- and diastereoselective TiCl4-mediated vinylogous Mukaiyama aldol reaction using the chiral vinylketene silyl N,O-acetal has been developed. The present vinylogous Mukaiyama aldol reaction provides a unique and effective means of controlling remote asymmetric induction. The methyl group at the alpha-position is important in achieving a high level of stereoselectivity. From a synthetic point of view, this methodology can provide a one-step construction of delta-hydroxy-alpha,gamma-dimethyl-alpha,beta-unsaturated carbonyl unit that is seen in many natural polyketide products.     

Non-destructive analysis of the two subspecies of African elephants, mammoth, hippopotamus, and sperm whale ivories by visible and short-wave near infrared spectroscopy and chemometrics

Visible (VIS) and short-wave near infrared (SW-NIR) spectroscopy was used for non-destructive analysis of ivories. VIS-SW-NIR (500-1000 nm) spectra were measured in situ for five kinds of ivories, that is two subspecies of African elephants, mammoth, hippopotamus, and sperm whale. Chemometrics analyses were carried out for the spectral data from 500 to 1000 nm region. The five kinds of ivories were clearly discriminated from each other on the scores plot of two principal components (PCs) obtained by principal component analysis (PCA). It was noteworthy that the ivories of the two subspecies of African elephants were discriminated by the scores of PC 1. The loadings plot for PC 1 showed that the discrimination relies on the intensity changes in bands due to collagenous proteins and water interacting with proteins. It was found that the scores plot of PC 2 is useful to distinguish between the ivories of the two subspecies of African elephants and the other ivories. We also developed a calibration model that predicted the specific gravity of five kinds of ivories from their VIS-SW-NIR spectral data using partial least squares (PLS)-1 regression. The correlation coefficient and root mean square error of cross validation (RMSECV) of this model were 0.960 and 0.037, respectively.     

Magnetic ordering of dangling bond networks on hydrogen-deposited Si(111) surfaces

Based on total-energy electronic-structure calculations within the density-functional theory, we find that a high spin state is realized for an ultimate dangling bond unit on an otherwise hydrogen-covered Si(111) surface. We further propose a systematic method of constructing nanometer-scale dangling bond networks that exhibit the ferrimagnetic spin ordering. The interplay between the electron-electron interaction and the surface reconstruction is elucidated.     

In vivo mapping of functional domains and axonal connectivity in cat visual cortex using magnetic resonance imaging

Noninvasive cognitive neuroimaging studies based on functional magnetic resonance imaging (fMRI) are of ever-increasing importance for basic and clinical neurosciences. The explanatory power of fMRI could be greatly expanded, however, if the pattern of the neuronal circuitry underlying functional activation could be made visible in an equally noninvasive manner. In this study, blood oxygenation level-dependent (BOLD)-based fMRI and diffusion tensor imaging (DTI) were performed in the same cat visual cortex, and the foci of fMRI activation utilized as seeding points for 3D DTI fiber reconstruction algorithms, thus providing the map of the axonal circuitry underlying visual information processing. The methods developed in this study will lay the foundation for in vivo neuroanatomy and the ability for noninvasive longitudinal studies of brain development.     

A new strategy for the design of water-soluble synthetic receptors: specific recognition of DNA intercalators and diamines

Water-soluble zinc bisporphyrin receptors 1 and 2 having two Lewis acidic sites (zinc) in the hydrophobic environment consisting of alkyl chains and a bisporphyrin framework, and covered with hydrophilic exterior (twelve or eighteen carboxyl groups) were prepared. The receptors show high affinity for diamines and DNA intercalators in water where the binding constants K(a) are of the order of 10(7) and 10(8) M(-1), respectively. Diamines and DNA intercalators are bound to the receptor through different mechanisms. Diamines are bound through hydrophobic interactions and zinc-nitrogen interactions, while DNA intercalators are bound through hydrophobic interactions and charge-transfer interactions. Flexible alkyl chains can make van der Waals contact with guests and create a hydrophobic environment around the bound guest by an induced-fit-type mechanism. For the binding of DNA intercalators, the following features are noteworthy: 1). Binding constants are similar between the zinc porphyrins and zinc-free porphyrins; 2). the binding constant is larger for the guest having the lower LUMO; this indicates the important contribution of charge-transfer interactions to binding; 3). the hydrophobic and cationic nature of DNA intercalators is substantially important, and 4). higher ionic strength reduced the binding affinities; this shows a moderate contribution of electrostatic interactions. The conformational instability of the receptors also contributes to the tight binding: hydrophobic and electrostatic interactions cannot both be favorable at the same time in the guest-free receptor. Enthalpy-entropy compensation observed for the binding of diamines and DNA intercalators is characterized by a relatively small slope (alpha=0.74) and a large intercept (beta=7.75 kcal mol(-1)) in the DeltaH degrees versus TDeltaS degrees plot; this shows that a conformational change of receptors and a significant desolvation occur upon binding. The receptor can competitively bind to propidium iodide to deprive DNA of the intercalated propidium iodide. These features of water-soluble receptors consisting of a rigid framework and flexible side chains with a large solvent-accessible area are in contrast to highly preorganized rigid receptors, and they can provide useful guidelines for rational design of induced-fit artificial receptors in water.     

Electron transport with mobility above 10–3 cm2/Vs in amorphous film of co‐planar bipyridyl‐substituted oxadiazole

We demonstrate that a bipyridyl substituted oxadiazole (Bpy‐OXD) shows high electron mobility that reached above 10^–3 cm²/Vs. We believe that the high mobility results from both the hybrid molecular structure of the two electron‐accepting units: bipyridyl and oxadiazole, and the planar molecular structure based on its lack of sterically hindered bulky substituent. The computational analysis elucidates that the amorphous nature of Bpy‐OXD in thin‐film state probably results from the polymorphic effect in isolated state and the volume effect in solid state. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Molecular Origin for the Thermal Stability of Rice Amylopectin 1

Abstract

The non-Newtonian behavior and dynamic viscoelasticity of Takanari and Reimei amylopectin solutions were measured with a rheogoniometer. The Takanari and Reimei amylopectin showed plastic behavior at a concentration above 2.0% at 25 °C. The viscosity of Takanari amylopectin decreased a little with increasing temperature at 2.0%. However, a little increase in the viscosity was observed with increasing temperature from 0 to 15 °C, then it stayed at a constant value with further increase in the temperature up to 80 °C at a concentration above 4.0%. An increase in the viscosity was also observed in Reimei amylopectin solution at various concentrations. The dynamic viscoelasticity of Takanari amylopectin increased with increasing concentration at low temperature (0 °C) and it stayed at a constant value with increasing temperature up to 80 °C. On the other hand, dynamic viscoelasticity for Reimei amylopectin showed a weak sigmoid curve. The tan δ of both amylopectins showed low values, 0.32-0.38, at low temperature range and kept constant with increasing temperature up to 80 °C. A little decrease of dynamic modulus of Takanari and Reimei amylopectin was observed upon addition of urea (4.0 M). The dynamic modulus of Takanari and Reimei amylopectin solution decreased rapidly when the temperature reached 45 and 60 °C, which was estimated to be a transition temperature, in 0.10 N NaOH solution. The molecular origin for the thermal stability of rice amylopectin (Takanari and Reimei) was essentially attributed to intramolecular associations in aqueous solution. Possible mode of intramolecular hydrogen bonding and van der Waals forces of attraction of amylopectin molecules are proposed.

     

Peumusolide A, unprecedented NES non-antagonistic inhibitor for nuclear export of MEK

A new polyketide peumusolide A was disclosed as an unprecedented NES non-antagonistic inhibitor for nuclear export of MEK, a promising scaffold for antitumor agents with novel mechanism of action, from Peumus boldus Molina. The absolute stereostructure as well as optical purity was established by use of the two synthesized enantiomeric model lactones. In addition, the Δε values in their CD spectra were demonstrated to be the conclusive index for determination of not only configuration at C-3 but also optical purity of natural congeneric polyketides. Peumusolide A was revealed to show NES non-antagonistic action by the biotinylated probe and to inhibit proliferation of MEK-activated tumor cells selectively.