不同岩蔷薇浸膏挥发性致香成分的SED-GC-MS分析研究

岩蔷薇(cistusladaniferusL.)又名赖百当(labdanum),属半日花科。利用其树脂分泌物及枝叶,通过蒸馏、浸提和萃取等方法,可制得岩蔷薇精油、浸膏、净油、油树脂等各种香原料品种。岩蔷薇的香原料制品是膏香类的极重要品种,主要应用于日化和食品行业,在烟草行业也多有应用。因香料烟香味的主要来源是类赖百当化合物的降解,故被归为烟草的五大类香味物质之一:赖百当类、双萜烯及其降解产物类。这类物质在香料烟中的含量较高,对形成香料烟的特殊香味风格具有重要意义,且在烟草中赖百当仅存在于香料烟中,烤烟、自肋烟中均不存在。赖百当类化合物是香料烟中特有的香气物质,主要成分是冷杉醇、赖百当烯二醇,经调制和醇化转化为多种降赖百当类化合物,其中降龙涎香醚、龙涎香内酯、脱氢龙涎香内酯等都具有强烈的龙涎香香气,对增进卷烟香气和吃味有很好作用。     

Gas-phase structure, conformation, and sulfur 2p photoelectron spectroscopy of pentafluorosulfur fluorosulfonate, SF5OSO2F

The structure of SF(5)OSO(2)F has been investigated using gas-phase electron diffraction and quantum-chemical calculations. It is found to exist primarily in the gauche form (SF(5) group gauche relative to the S-F bond of the SO(2)F group with phi(S-O-S-F = 71(7) degrees ). A small contribution of the trans conformer cannot be excluded. Photoelectron spectroscopy gives ionization energies for the sulfur 2p electrons that reflect the relative electronegativities of fluorine and oxygen. The widths of the peaks in the photoelectron spectra indicate that there is considerable vibrational excitation associated with the core ionization of the sulfur atoms.     

Observation of quantum coherence in mesoscopic molecular magnets

By applying a transverse magnetic field B( perpendicular) of sufficient strength to the uniaxial molecular magnets Fe8 and Mn12, the tunneling splitting Delta(t) of their S = +/-10 magnetic ground states can be made large compared to perturbations such as hyperfine and dipolar interactions. We present evidence for such a Delta(t) from magnetic specific heat data below 1 K that is consistent with coherent quantum mechanical tunneling in a "mesoscopic" system under such conditions.     

Chemical insights from high-resolution X-ray photoelectron spectroscopy and ab initio theory: propyne, trifluoropropyne, and ethynylsulfur pentafluoride.

High-resolution carbon 1s photoelectron spectroscopy of propyne (HC triple bond CCH3) shows a spectrum in which the contributions from the three chemically inequivalent carbons are clearly resolved and marked by distinct vibrational structure. This structure is well accounted for by ab initio theory. For 3,3,3-trifluoropropyne (HC triple bond CCF3) and ethynylsulfur pentafluoride (HC triple bond CSF5), the ethynyl carbons show only a broad structure and have energies that differ only slightly from one another. The core-ionization energies can be qualitatively understood in terms of conventional resonance structures; the vibrational broadening for the fluorinated compounds can be understood in terms of the effects of the electronegative fluorines on the charge distribution. Combining the experimental results with gas-phase acidities and with ab initio calculations provides insights into the effects of initial-state charge distribution and final-state charge redistribution on ionization energies and acidities. In particular, these considerations make it possible to understand the apparent paradox that SF5 and CF3 have much larger electronegativity effects on acidity than they have on carbon 1s ionization energies.     

Reactivity and core-ionization energies in conjugated dienes. Carbon 1s photoelectron spectroscopy of 1,3-pentadiene

The high-resolution carbon 1s photoelectron spectrum of trans-1,3-pentadiene has been resolved into contributions from the five inequivalent carbon atoms, and carbon 1s ionization energies have been assigned to each of these atoms. Spectra have also been measured for propene and 1,3-butadiene at better resolution than has previously been available. The ionization energies for the sp2 carbons are found to correlate well with activation energies for electrophilic addition and with proton affinities. Comparing the results for 1,3-pentadiene with those for ethene, propene, and 1,3-butadiene as well as with results of theoretical calculations makes it is possible to assess the effect of the terminal methyl group in 1,3-pentadiene. As in propene, the methyl group contributes electrons to the beta carbon through the pi system. In addition, there is a significant (though smaller) contribution from the methyl group to the terminal (delta) CH2 carbon, also through the pi system. Most of the effect of the methyl group is present in the ground-state molecule. There are only relatively small contributions from the methyl group to the ionization energies from redistribution of charge in the pi system in response to the removal of a core electron. In addition to these specific effects, there is an overall decrease in average ionization energy as the size of the molecule increases as well as effects that are specific to the conjugated systems in 1,3-butadiene and 1,3-pentadiene. The results provide insight into the reactivity and regioselectivity of conjugated dienes.     

Gas phase ESCA studies of trithiapentalene and its 2,5-dimethyl derivative

1,6,6a-trithiapentalene and its 2,5-dimethyl derivative have been studied in the gas phase by means of ESCA in order to elucidate the unusual type of S---S bonding in these molecules. The high resolution spectra show very wide S 2p lines from the terminal sulfur atoms due to vibrational broadening. The effect of core ionization on the S---S bond lengths in trithiapentalene has been estimated using the equivalent core approximation and the CNDO/2 method. Ground and final state potential curves have been calculated and explain qualitatively the differences in line widths for the terminal and central sulfur atoms. The observed chemical shifts agree with predictions from CNDO/2 and ab initio calculations.