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.     

Bis

[formula: see text] The generation of (2-PyMe2Si)2CHLi was easily accomplished by the deprotonation of (2-PyMe2Si)2CH2 using n-BuLi in Et2O. Thus generated (2-PyMe2Si)2CHLi was found to react with a variety of aldehydes and ketones to give the corresponding vinylsilanes in extremely high yields with complete stereoselectivities.     

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.     

A new biodegradable polydepsipeptide microsphere for application in drug delivery systems

A sequential polydepsipeptide containing a tripeptide sequence L-alanyl-Lalanyl-ethyl L-glutamyl and an-hydroxy acid L-lactic acid, poly(Ala-Ala-Glu(OEt)-Lac), was synthesized to prepare the microspherical particles by the solvent evaporation process. In this case, the solvents play the most important role for the preparation of polydepsipeptide microspheres and, as an example, when 200 mg of the polydepsipeptide dissolved in 10 ml of 98/2% chloroform/dichloroacetic acid mixture was stirred at 400 rpm and 30 C, the microspherical particles with mean diameter of 58m were formed after pouring into 200 ml of 1% (w/v) poly(vinyl alcohol) solution. 17-Estradiol was incorporated into the particles, and the resulting particles were found to contain 5 mg of drug per 25 mg of the particle. The in vivo release of drug from the microspherical formulation was evaluated by measuring the pharmacological influence on rat prostate. It was found that the sufficient amount of drug, keeping the effective pharmacological influence, is supplied during the first 12-week period, followed by an incomplete supplying of drug intil the implant is perfectly degraded in vivo in the 25th week from the start of implantation.     

TG-DTA/FT-IR method for analyzing thermal decomposition mechanism of polyesters

An attempt to estimate the thermal decomposition mechanism of polymers using the simultaneous TG-DTA/FT-IR system was summarized. The library search of FT-IR spectra at various temperatures and of the subtraction spectrum obtained by subtracting the spectra at different temperatures were used to determine the types of evolved gases from poly(ethylene terephthalate) and poly(butylene terephthalate) at given stages of decomposition. The quantitative analysis of evolved gases was carried out using the specific gas profiles at the specific absorption band. The kinetic parameters were estimated from both TG and spectroscopic curves measured at various heating rates.