Structure of excited states in Se-isotopes

Energy systematics of the anomalously low-lying excited 0⁺ states and the systematic behaviour of theB(E2: 0⁺→2 ₁ ⁺ ) values in Se-isotopes are investigated by taking the important effect of mutual interplay between dynamical pairing and quadrupole correlations into account.     

Suppression of moiré fringes due to sampling of halftone screened images

When a halftone screened image is discretely sampled by, for example, a CCD array, moiré fringes sometimes appear. These moiré fringes are caused by aliasing errors due to the improper sampling rate. To suppress these fringes, a dual sampling method is proposed. In this method, halftone screened images are sampled twice with different sampling rates, and the selection of proper frequency components less suffering from aliasing errors can effectively suppress moiré fringes.     

Chemically driven nonlinear waves and oscillations at an oil-water interface

An experimental investigation is presented of chemically driven dynamic instability of an oil-water interface in a cylindrical and annular glass container. The immiscible liquids are water containing a surfactant (TSAC) and nitrobenzene containing iodine. The reaction at the interface leads to complex deformation patterns including rotating solitary waves, multiple wave trains, periodic and nonperiodic oscillations, source-to-sink propagation, and intermittent behavior. A phase diagram is established for the two solute concentrations ranging from 10^-4 to 10^-1 M. It shows five distinct regions of different dynamic regimes, determined by interaction of at least three mechanisms: dynamic wetting of the container wall, capillary effect, and Marangoni instability of the liquid-liquid interface. The influences of aspect ratio, concentration product, and temperature are investigated and local time traces are derived from electropotential differences. Their spectral analysis reveals details of periodic or irregular motion. Transitions between the dynamic modes of the system during its temporal evolution are recorded. Quantitatively determined profiles of regular waves are analyzed by exponential functions and a simple model for this is proposed.     

Autocatalytic domino Michael reaction leading to bicyclo[2.2.2]octane-2,5-dione derivatives

In the presence of a catalytic amount of lithium amide, the reaction of oxophorone with electron-deficient olefins afforded bicyclo[2.2.2]octane-2,5-dione derivatives in high yields. The reaction proceeds autocatalytically by an enolate of bicyclo[2.2.2]octane-2,5-dione, generated by an initial domino Michael reaction.     

Theoretical study of environmental effects on proton transfer reaction through the peptide bond in a model system

This study considered the possibility of proton transfer reactions through the peptide bond under different environments using the dipeptide and the 12-mer polyglycine α-helix models, in which diglycine is substituted by the 12-mer polyglycine helix. Ab initio molecular orbital calculations were carried out at the B3LYP/6-31+G(d) level of theory. To evaluate the free energies in solution, calculations of the solvation energies were performed using PCM. The correction functions on the calculated solvation energies were provided to reproduce experimental pKa values. The proton transfer reactions through the peptide bond are concluded to be possible in the protein for a wide range of proton acceptors. His complex has two free energy minima along a putative proton transfer pathway in spite of one minimum in the other complexes. The α-helix is estimated to suppress the proton transfer reactions through the peptide bond at the termini of the helix, although it is possible to proceed when the proton affinity of the acceptor is low. Contribution to the Mark S. Gordon 65th Birthday Festschrift Issue.     

An improved method for basic hydrolysis of isoflavone malonylglucosides and quality evaluation of Chinese soy materials

Basic hydrolysis procedure is often included in the sample preparation in order to quantify malonylglucosides or acetylglucosides of soy materials. However, it is preferable not to use NaOH as a hydrolytic reagent considering the effect of its alkalinity on the successive injection to HPLC and low acidity of soy isoflavones. This paper presents an improved method for basic hydrolysis using ammonia as a hydrolytic reagent without the additional neutralization step. Moreover, by means of HPLC and LC-MS methods, a systematic quality evaluation of natural soy materials from Chinese markets were established and discussed, inclusive of soybeans, black soybeans, defatted soy flours, as well as the distribution of isoflavones in the seed coat, hypocotyl and cotyledon. The results indicate that HPLC profiling patterns of originating various isoflavone constituents of Chinese soybeans was similar to those of Japanese ones, and those of Chinese black soybeans was similar to those of American ones. The average content level of total soy isoflavones of Chinese soybeans and black soybeans were a little lower than that of American and Japanese ones. Additionally, the thorough analysis for Semen Sojae Praeparatum, a Chinese herbal medicine made from fermented black soybeans or soybeans was done for the first time and the characteristic of its HPLC profiling patterns shows the higher content of isoflavone glucosides and aglycones than those of natural soy materials.     

Resolution of overlapped chromatograms by means of the kalman filter : Dimensional reduction of error covariance matrices and state estimate vectors

If many samples are successively injected into a high-performance liquid chromatograph at short intervals, then overlapped chromatograms will be obtained. A simplified version of the Kalman-filter algorithm is described for rapid resolution of several such overlapped peaks on small laboratory computers; the dimensionalities of the error covariance matrix Pk and state estimate vector X?k are reduced to far less than the total number of the peaks. Computer simulation shows that at least twenty partially overlapped Gaussian peaks, used as a model of the successive injections can be successfully resolved, with the 4 × 4 matrix Pk and 4-vector X?k. This version is independent of the number of injections and is effective for the resolution of a finite number of peaks in that injection mode. The algorithm of small dimensions is applicable to a wide variety of peak resolution procedures.     

General asymmetric hydrogenation of alpha-branched aromatic ketones catalyzed by TolBINAP/DMAPEN-ruthenium(II) complex

[reaction: see text] A catalyst system consisting of RuCl2[(S)-tolbinap][(R)-dmapen] and t-C4H9OK in 2-propanol effects asymmetric hydrogenation of arylglyoxal dialkylacetals to give the alpha-hydroxy acetals in up to 98% ee. Hydrogenation of racemic alpha-amidopropiophenones under dynamic kinetic resolution predominantly gives the syn alcohols in up to 99% ee and >98% de, while the reaction of racemic bezoin methyl ether gives the anti alcohols in excellent stereoselectivity.