Spectral analysis of scattered light from flowers’ petals

A new method was developed for studying absorption characteristics of opaque samples based on the light scattering spectroscopy. Measurements were made in white, red and violet petals of Petunia hybrida, and gave the absorption spectra in a non-destructive manner without damaging the cell structures of the petal. The red petal has absorption peak at 550 nm and the violet has three absorption peaks: at 450, 670, and 550 nm. The results were discussed in correlation with the microscopic cell structures of the petal observed with optical microscope and transmission electron microscopy (TEM). Only the cells placed in the surface have the pigments giving the color of the petal.     

Temperature-responsive polymers in mixed solvents: competitive hydrogen bonds cause cononsolvency

If two good solvents become poor for a polymer when mixed, the solvent pair is called a cononsolvent pair. The sharp reentrant coil-to-globule-to-coil transition of a poly(N-isopropylacrylamide) chain observed in the mixed solvent of water and methanol is shown to be caused by the competitive hydrogen bonding by water and methanol molecules onto the polymer chain. On the basis of a new statistical-mechanical model for competitive hydrogen bonds, the mean square end-to-end distance is theoretically calculated and compared with experiment. The chain sharply collapses at the molar fraction xm approximately 0.2 of methanol, stays collapsed up to xm approximately 0.4, and finally recovers the swollen state at xm approximately 0.6. Such a reentrant coil-globule transition takes place because the total number of hydrogen bonds along the chain exhibits a similar square-well-type depression as a result of the competition.     

Effects of added surfactants on thermoreversible gelation of associating polymer solutions

The influence of added surfactants on physical properties of associating polymer solutions was examined by a new statistical‐mechanical theory of associating polymer solutions with multiple junctions and by computer simulation. The sol–gel transition line, the spinodal line, and the number of elastically effective chains in the mixed networks were calculated as functions of the concentration of added surfactants. All of them exhibited nonmonotonic behavior as a result of the following two competing mechanisms. One was the formation of new mixed micelles by binding surfactants onto the polymer associative groups. These micelles serve as crosslink junctions and promote gelation. The other was the replacement of polymer associative groups in the already formed network junctions by added surfactants. Such replacement lowers connectivity of junctions and destroys networks. The critical micelle concentration was also calculated. The results are compared with the reported experimental data on poly(ethylene oxide)‐based associating polymers and hydrophobically modified cellulose derivatives. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 733–751, 2004     

Loss of regularity for the solutions to hyperbolic equations with non‐regular coefficients—an application to Kirchhoff equation

We consider the Cauchy problem for second‐order strictly hyperbolic equations with time‐depending non‐regular coefficients. There is a possibility that singular coefficients make a regularity loss for the solution. The main purpose of this paper is to derive an optimal singularity for the coefficient that the Cauchy problem is C^∞ well‐posed. Moreover, we will apply such a result to the estimate of the existence time of the solution for Kirchhoff equation. Copyright © 2003 John Wiley & Sons, Ltd.     

Application of atomic stereomicroscope to surface science

A stereograph of atomic arrangement was displayed directly on the screen of display-type spherical-mirror analyzer without any computer-aided conversion process for the first time. This stereoscopic photograph enables viewing three-dimensional atomic arrangement. This technique was realized taking advantage of the phenomenon of circular dichroism in photoelectron angular distribution. The azimuthal shifts of forward focusing peaks in a photoelectron angular distribution taken with left and right helicity light in a special arrangement are the same as the parallaxes in a stereo view of atoms. Hence a stereoscopic recognition of three-dimensional atomic arrangement is possible, when the left eye and the right eye respectively view the two images obtained by left and right helicity light simultaneously.     

One-step preparation of 3-alkoxypyrazine-2-carbonitriles from pyrazine-2,3-dicarbonitriles and related reactions

A series of 5,6-disubstituted 3-alkoxypyrazine-2-carbonitriles ( 2a-i ) were prepared from 5,6-disubstituted pyrazine-2,3-dicarbonitriles ( 1a-d ) by direct substitution with alcohols. Treatment of 1 with amines gave either pyrrolopyrazines ( 3a,b ) or substitution products ( 4,5 ). In a low temperature range, 1 afforded imidates and related compounds ( 6–11 ). The preference among these reactions depended on the 5,6-substituents and on the reaction conditions.     

Headspace solid-phase microextraction-gas chromatography--mass spectrometry analysis of the volatile compounds of Evodia species fruits

In this study the investigation of the aroma compounds of dried fruits of Evodia rutaecarpa (Juss.) Benth. and E. rutaecarpa (Juss.) Benth. var. officinalis (Dode) Huang (i.e. E. officinalis Dode) (Rutaceae family) was carried out to identify the odorous target components responsible for the characteristic aroma of these valuable natural products. To avoid the traditional and more time-consuming hydrodistillation, the analyses were carried out by means of headspace solid-phase microextraction (HS-SPME) coupled to gas chromatography-mass spectrometry (GC-MS). The SPME headspace volatiles were collected using a divinylbenzene-carboxen-polydimethylsiloxane (DVB-CAR-PDMS) fiber. The extraction conditions were optimized using a response surface experimental design to analyze the effect of three factors: extraction temperature, equilibrium time and extraction time. The best response was obtained when the extraction temperature was around 80 degrees C, equilibrium time near 25 min and extraction time close to 18 min. Analyses were performed by GC-MS with a 5% diphenyl-95% dimethyl polysiloxane (30 m x 0.25 mm I.D., film thickness 0.25 microm) capillary column using He as the carrier gas and a programmed temperature run. The main components of the HS-SPME samples of E. rutaecarpa (concentration >3.0%) were limonene (33.79%), beta-elemene (10.78%), linalool (8.15%), myrcene (5.83%), valencene (4.73%), beta-caryophyllene (4.62%), linalyl acetate (4.13%) and alpha-terpineol (3.99%). As for E. officinalis, the major compounds were myrcene (32.79%), limonene (18.36%), beta-caryophyllene (9.92%), trans-beta-ocimene (6.04%), linalool (5.88%), beta-elemene (7.85%) and valencene (4.62%).     

Stereospecific epoxide-opening reactions of 1,1-dibromo-3,4-epoxy-1-alkenes with carbon nucleophiles

The stereospecific epoxide-opening reactions of 1,1-dibromo-3,4-epoxy-1-alkenes with allyltributylstannane and with ketene silyl acetals in the presence of a Lewis acid are described. Both the reactions occurred regioselectively at the allylic position via an S_N2 process giving rise to a single product, respectively. Treatment of the products by the latter reaction with p-TsOH afforded various 3,4-anti- and 3,4-syn-disubstituted γ-lactones in a highly stereoselective manner and high yields.