A novel synthesis of (E)-3,7-dimethyl-2-octene-1,8-diol secreted by the african monarch using the ring-opening reaction of α-methyl-β-propiolactone

The regioselective ring-opening reaction of α-methyl-β-propiolactone with 3,3-ethylene-dioxybutylmagnesium bromide in the presence of copper(I) catalyst afforded 2-methyl-6-oxoheptanoic acid, which was easily converted into (E)-3,7-dimethyl-2-2-octene-1,8-diol in good yield.     

A novel method for the terpene synthesis by the ring-opening reaction of β-methyl-β-propiolactone

A new route for the terpene synthesis is investigated, which undergoes via terpene carboxylic acids as key intermediates obtained by the regiospecific ring opening of β-methyl-β-propiolactone with a cuprate or with a Grignard reagent in the presence of a copper catalyst.     

The fluorescence excitation spectrum of aniline in a supersonic free jet: Double minimum potential for the inversion vibration in the excited state

The fluorescence excitation spectrum of the first singlet transition of aniline in a supersonic free jet has been measured. Vibronic transitions involving the inversion vibration of the NH₂ group in the excited state have been observed. The double minimum potential function in the excited state has been determined from the observed vibrational levels.     

Angular distribution of different vibrational components of the X and B states reached after resonant Auger decay of core-excited H2O: experiment and theory

Vibrationally resolved spectra have been obtained for the lowest-lying cationic states X (2)B(1), A (2)A(1), and B (2)B(2) of the water molecule reached after participator resonant Auger decay of core-excited states. The angular distribution has been measured of the first four vibrational components of the X state in the photon energy regions including the O 1s-->4a(1) and the O 1s-->2b(2) core excitations, and for different portions of the vibrational envelope of the B state in the photon energy region including the O 1s-->2b(2) core excitation. For the X state, a large relative spread in beta values of the different vibrational components is observed across both resonances. For the B state, a very different trend is observed for the high binding energy side and the low binding energy side of the related spectral feature as a function of photon energy. A theoretical method based on the scattering K matrix has been used to calculate both the photoabsorption spectrum and the beta values, by taking both interference between direct and resonant photoemission and vibrational/lifetime interference into account. The numerical results show qualitative agreement with the trends detected in the experimental values and explain the conspicuous variations of the beta values primarily in terms of coupling between direct and resonant photoemission by interaction terms of different sign for different final vibrational states.     

Photoexcitation of dimethyl sulfide and dimethyl disulfide in the vacuum ultraviolet region: Rydberg states and photofragment emissions

Photoabsorption cross sections and fluorescence excitation spectra of dimethyl sulfide (DMS) and dimethyl disulfide (DMDS) vapors have been studied in the 110–220 nm region using synchrotron radiation. For DMS, a new Rydberg series originating from the n_s orbital is identified. A number of broad bands from DMDS are assigned as Rydberg transitions. Emissions from DMS and DMDS are assigned as the CH₃( - ) band. For DMDS, another emission which is attributable to the S₂(B-X) band appears in the excitation below 125 nm. Photodissociation processes forming the excited fragments are discussed.     

Photodissociation investigation of doubly charged ethanol clusters induced by inner-shell electron ionization

Fragmentation of doubly charged ethanol clusters [(C(2)H(5)OH)(n)] following the O 1s ionization has been investigated by means of the photoelectron-photoion-photoion coincidence (PEPIPICO) method. The dominant fission channel of (C(2)H(5)OH)(n)(2+) was the formation of protonated cluster ion pairs [H(C(2)H(5)OH)(l)(+)/H(C(2)H(5)OH)(m)(+)]. The fragmentation mechanisms of these ion pairs were discussed based on the analysis of the PEPIPICO contour shape. It was clarified that the prominent fragmentation channel was a secondary decay mechanism, where neutral evaporation occurs after charge separation. On the other hand, the formation of small fragment ions was suppressed, excluding the formation of certain specific fragments (H(3)O(+), C(2)H(5)(+)/COH(+), and C(2)H(4)OH(+)). The formation of small fragment ions was suppressed due to the cooling effect caused by the neutral evaporation and the decrease in the electrostatic repulsive force caused by charge separation.     

Production of methyl-oxonium ion and its complexes in the core-excited (HC(O)OCH3)n clusters: H/H+ transfer from the alpha carbonyl

Dissociation of free methyl-formate (MF), HC(O)OCH3, and its clusters (MF)n, (HC(O)OCH3)n, induced by core-level excitation was studied near the oxygen K edge by time-of-flight fragment-mass spectroscopy. Besides the protonated clusters, (MF)nH+ with n < or = 15, we identified the production for another series of (MF)mCH3OH2+ with m < or = 14 as well as methyl-oxonium ion, CH3OH2+, characteristic of hydrogen transfer reactions in the cationic clusters. Here; specifically labeled methyl-formate-d (MFD), DC(O)OCH3 was also used to examine the core-excited dissociation mechanisms. Deuterium-labeled experiments indicated that MFD+ with low internal energies, partially generated after the core excitation, produces CH3OD+ via a site-specific deuterium transfer from the alpha carbonyl in the molecular cation and that CH3OD2+ can be formed via the successive transfer of another deuterium from the neighbor molecule in the clusters. The deuteron (proton) transfer was also found to take place preferentially from the alpha carbonyl of the neighbor molecule for the production of deuteronated (MFD)nD+, (protonated (MF)nH+), clusters. The minimal energy requirement paths were examined for dimer (MF)2+ cation to support the present dissociation mechanisms of core-excited (MF)n clusters using ab initio molecular-orbital calculations.     

Mass spectroscopic approach to amino acids formation processes by UV irradiation to simple organic molecules in aqueous solution.

We have studied amino acid formation by UV (193 nm) irradiation to organic molecules (amines, alcohols and amides) in aqueous solution. Among several types of detected amino acids, small aliphatic amino acids (Gly and alpha-, beta-Ala and alpha-, beta-, gamma-ABA) were quantitatively identified. Among these small aliphatic amino acids, certain amino acids were formed in its free form, even before hydrolysis, contrary to the results of UV irradiation to a gas mixture of CO, NH3, and H2O, where amino acids were hardly detected before hydrolysis. The species distribution of identified amino acids showed a dependence on the starting organic molecules, and also on the presence of ammonia. The formation processes of the identified small aliphatic amino acids were investigated with the aid of electrospray ionization (ESI) MS and MS/MS measurements of photoproducts. Possible formation processes of these amino acid precursors from each starting molecules are proposed. By identifying the amino acid precursor, which has a chiral carbon atom, a new possibility is suggested for asymmetric photosynthesis of amino acid from achiral organic molecules.     

Permeation of complexed metal ions through a hydrophobic membrane

Selective concentration of a heavy metal complex with acetylacetone (acac) through a hydrophobic polystyrene membrane was carried out under a pressure gradient. A chelate forming heavy metal was selectively concentrated about 2 fold by this method. When using a coating membrane with a high water flux, the permeabilities increased with increasing complex fraction in the aqueous solution, while using a membrane with a low water flux, a bulky complex was not highly concentrated because of steric hindrance. The complex partitioned on the membrane surface was transported and concentrated under a pressure gradient and a linear relationship was found to exist between permeabilities and partition coefficients. It will be possible to concentrate hydrophobic organic solutes by this method, for acac was concentrated when the Cu—acac complex was formed. As the permeabilities increased with decreasing pressure and membrane compaction was strong for a coating membrane, it seems effective to permeate at a low pressure.     

Hydrogen bonding in methanol clusters probed by inner-shell photoabsorption spectroscopy in the carbon and oxygen K-edge regions

Hydrogen bonding in methanol clusters has been investigated by using inner-shell photoabsorption spectroscopy and density functional theory (DFT) calculations in the carbon and oxygen K-edge regions. The partial-ion-yield (PIY) curves of H(CH(3)OH)(n)(+) were measured as the soft x-ray absorption spectra of methanol clusters. The first resonance peak in the PIY curves, which is assigned to the sigma*(O-H) resonance transition, exhibits a 1.20 eV blueshift relative to the total-ion-yield (TIY) curves of molecular methanol in the oxygen K-edge region, while it exhibits a shift of only 0.25 eV in the carbon K-edge region. Decreased intensities of the transitions to higher Rydberg orbitals were observed in the PIY curves of the clusters. The drastic change in the sigma*(O-H) resonance transition is interpreted by the change in the character of the sigma*(O-H) molecular orbital at the H-donating OH site due to the hydrogen-bonding interaction.