Structural determination of carvone, a component of spearmint, by means of gas electron diffraction augmented by theoretical calculations

The molecular structure and conformation of carvone, a compound with a minty odor, were investigated by means of gas electron diffraction supported by theoretical calculations. Electron diffraction patterns were recorded by heating the nozzle up to 128 °C to obtain enough scattering intensity. The infrared spectrum was also measured by using an absorption cell with a path length of 10 m. The obtained molecular scattering intensities were analyzed with the aid of theoretical calculations and infrared spectroscopy. It was revealed that the experimental data are well reproduced by assuming that carvone consists of a mixture of three conformers that have the isopropenyl group in the equatorial position and mutually differ in the torsional angle around the single bond connecting the ring and the isopropenyl group. It was also found that the puckering amplitude of the ring of carvone is close to those of menthol and isomenthol, a minty compound and its nonminty isomer. The determined structural parameters (r_g and ∠_α) of the most abundant conformer of carvone are as follows: 〈r(C-C)〉=1.520(3) Å; 〈r(CC)〉=1.360(5) Å; r(CO)=1.225(5) Å; 〈r(C-H)〉=1.104(4)Å; 〈∠CC-C〉=121.1(5)°; 〈∠C-C-C〉=110.4(5)°; ∠C-CO-C=117.1(14)°; 〈∠C-C-H〉=111.1(13)°. Angle brackets denote average values and parenthesized values are the estimated limits of error (3σ) referring to the last significant digit.     

Enhancement of electronic excitation energy transfer in the colloidal crystals of colloidal silica suspensions doped with fluorescent dyes

The efficiency of electronic excitation energy transfer from photo-excited rhodamine 110 (Rh110, energy donor) to rhodamine B (RhB, energy acceptor) in an exhaustively deionized colloidal silica suspension has been studied. This colloidal suspension shows Bragg reflection due to the formation of colloidal crystals and the Bragg-peak wavelength is controllable by the volume fraction of the silica spheres. When the Bragg-peak wavelength matches with the fluorescence band of Rh110, a depletion was observed in the Rh110 fluorescence spectrum. This means the fluorescence of Rh110 is partially trapped due to the Bragg reflection inside the crystal lattice. In the coexistence of RhB, the enhancement of RhB fluorescence intensity was observed. These facts clearly indicate the trapped photon energy of Rh110 is efficiently transferred to RhB within the colloidal crystals. The quantitative measurements showed that the enhancement of the transfer efficiency is 20% (or slightly more) in the present experimental conditions.     

Substituent effects on the kinetics for the chemiluminescence reaction of 6-arylimidazo[1,2-a]pyrazin-3(7H)-ones (Cypridina luciferin analogues): support for the single electron transfer (SET)-oxygenation mechanism with triplet molecular oxygen

Kinetics of chemiluminescence reactions of 2-methyl-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one (1c, Cypridina luciferin analogue) and substituent effects of the 6-aryl group of derivatives 1 strongly suggest that the rate-determining step is a single electron transfer from an anion derived from 1 to a triplet molecular oxygen (O₂) in the oxygenation process.     

Solubility of α-amino acids in water under high pressure: glycine, -alanine, -valine, -leucine, and -isoleucine

The solubility of glycine, -alanine, -valine, -leucine, and -isoleucine in water was measured at 298.15 K and pressures up to 400 MPa. The standard deviation of the logarithm of the solubility is 0.001–0.003, equal to or better than the accuracy of atmospheric pressure measurement in the literature (0.001–0.05). A variety of solubility phenomena were observed. The solubility of glycine decreased with increasing pressure, whereas that of -alanine increased. The -valine and -isoleucine have a solubility maximum at around 100 MPa, and -leucine seems to exhibit a solid-phase phase transition at around 200 MPa. Pressure coefficient of the solubilities at 0.10 MPa is compared with that thermodynamically estimated in reference to aqueous density measurements of glycine and -alanine at 298.15 K and 0.10 MPa, supporting a reliability of our high-pressure measurements.