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Artemisinic acid labeled with both 13C and 2H at the 15-position has been fed to intact plants of Artemisia annua via the cut stem, and its in vivo transformations studied by 1D- and 2D-NMR spectroscopy. Seven labeled metabolites have been isolated, all of which are known as natural products from this species. The transformations of artemisinic acid—as observed both for a group of plants, which was kept alive by hydroponic administration of water and for a group, which was allowed to die by desiccation—closely paralleled those, which have been recently described for its 11,13-dihydro analog, dihydroartemisinic acid. It seems likely therefore that similar mechanisms, involving spontaneous autoxidation of the Δ4,5 double bond in both artemisinic acid and dihydroartemisinic acid and subsequent rearrangements of the resultant allylic hydroperoxides, may be involved in the biological transformations, which are undergone by both compounds. All of the sesquiterpene metabolites, which were obtained from in vivo transformations of artemisinic acid retained their unsaturation at the 11,13-position, and there was no evidence for conversion into any 11,13-dihydro metabolite, including artemisinin, the antimalarial drug, which is produced by A. annua. This observation led to the proposal of a unified biosynthetic scheme, which accounts for the biogenesis of many of the amorphane and cadinane sesquiterpenes that have been isolated as natural products from A. annua. In this scheme, there is a bifurcation in the biosynthetic pathway starting from amorpha-4,11-diene leading to either artemisinic acid or dihydroartemisinic acid; these two committed precursors are then, respectively, the parents for the two large families of highly oxygenated 11,13-dehydro and 11,13-dihydro sesquiterpene metabolites, which are known from this species. 相似文献
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Ethanol was found to give a metastable crystalline phase (crystal-II) when the liquid was cooled at a moderate rate. Glassy states of liquid and of newly found crystal-II were obtained in the calorimeter cell by controlling the cooling rate of the liquid. The heat capacities of these phases as well as that of the stable crystal-I were measured by an adiabatic calorimeter in the temperature range between 14 and 300 K. The glass transition temperature Tg, the heat-capacity jump at Tg, and the residual entropy were found to be 97 K, 35.3 J K?1 mol?1, and 8.93 J K?1 mol?1 for the glassy liquid, and 97 K, 22.8 J K?1 mol?1, and 4.24 J K?1 mol?1 for the glassy crystal-II, respectively. The values for the residual entropy are referred to the third-law entropy for crystal-I.The heat capacities reported previously for the supercooled liquid by Gibson et al. and by Parks and Kelley agree well with those for the metastable crystal-II. Those of the supercooled liquid connect smoothly with those obtained for the liquid above the melting temperature. Thus, ethanol is found to be another example of a low-molecular-weight compound which shows multiple glass-transition phenomena. 相似文献
5.
The present review deals primarily with glass transition phenomena in pure simple compounds and pays special attention to the thermodynamic aspects of the vitrification process. The concept of glassy state is extended to liquid crystalline and even to crystalline materials which have any type of disorder. Thus the familiar supercooled liquid-glass transition is shown to be just one example of a class of ‘glass transitions’ due to loss of equilibrium which must occur quite frequently in condensed matter. Evidence of several glass transition phenomena in one and the same compound is given. The fact that glass should be considered as one of the states of aggregation of matter, irrespective of either the method of formation or the existence of three-dimensional periodicity in molecular arrangements, is stressed. 相似文献
6.
Yi‐Ying Kao Chu‐Nian Cheng Sy‐Chyi Cheng Hsiu‐O Ho Jentaie Shiea 《Journal of mass spectrometry : JMS》2013,48(11):1129-1135
Electrospray laser desorption ionization mass spectrometry (ELDI/MS) was used to rapidly distinguish authentic banknotes from counterfeits of the US dollar and the New Taiwan dollar. The banknotes' surfaces were irradiated with a pulsed ultraviolet laser, after which the desorbed ink compounds entered an electrospray plume and formed ions via interactions with charged solvent species. Authentic banknotes were found to differ from their counterfeit equivalents in their surface chemical compositions. The detected chemical compounds included various polymers, plasticizers and inks; these results were comparable with those obtained using solvent extraction followed by electrospray ionization mass spectrometry analysis. Because of the high spatial resolution of the laser beam, ELDI/MS analysis resulted in minimal damage to the banknotes. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
7.
Daouda Ndiaye Maryame Sy Agns Pallier Sandra Même Isidro de Silva Sara Lacerda Aline M. Nonat Loïc J. Charbonnire va Tth 《Angewandte Chemie (International ed. in English)》2020,59(29):11958-11963
The search for more biocompatible alternatives to Gd3+‐based MRI agents, and the interest in 52Mn for PET imaging call for ligands that form inert Mn2+ chelates. Given the labile nature of Mn2+, high inertness is challenging to achieve. The strongly preorganized structure of the 2,4‐pyridyl‐disubstituted bispidol ligand L1 endows its Mn2+ complex with exceptional kinetic inertness. Indeed, MnL1 did not show any dissociation for 140 days in the presence of 50 equiv. of Zn2+ (37 °C, pH 6), while recently reported potential MRI agents MnPyC3A and MnPC2A‐EA have dissociation half‐lives of 0.285 h and 54.4 h under similar conditions. In addition, the relaxivity of MnL1 (4.28 mm ?1 s?1 at 25 °C, 20 MHz) is remarkable for a monohydrated, small Mn2+ chelate. In vivo MRI experiments in mice and determination of the tissue Mn content evidence rapid renal clearance of MnL1. Additionally, L1 could be radiolabeled with 52Mn and the complex revealed good stability in biological media. 相似文献
8.
Sy D. Friedman 《Proceedings of the American Mathematical Society》1999,127(12):3707-3709
We use ``iterated square sequences' to show that there is an -definable partition such that if is an inner model not containing :
- (a)
- For some is stationary.
- (b)
- For each there is a generic extension of in which does not exist and is non-stationary.
9.
Masanori Yoshikawa Michio Sorai Hiroshi Suga Syŭzŏ Seki 《Journal of Physics and Chemistry of Solids》1983,44(4):311-321
Heat capacity measurements have been made for six kinds of specimens prepared by different methods. Among them, Sample A exhibited a A-type ferromagnetic pahse transition at 1.347 K and a Schottky-type anomaly due to the zero-field splitting around 9K. The total entropy and enthalpy were (11.05 ± 0.04) J K?1mol?1 and (97.0 ± 0.4) J mol?1, respectively. Sample B exhibited a Sehottky-type anomaly around 0.4 K due to the ferro-magnetic dimeric coupling with as well as the Schottky-type anomaly at 9K. The total magnetic entropy and enthalpy were (11.45 ± 0.03) JK?1 mol?1 and (93.8 ± 0.8) J mol?1, respectively. The remaining samples are simple mixtures of the λ-type modification and the dimeric modification. Irrespective of the magnetic behavior at low temperatures, all the samples showed a non-magnetic first-order phase transition around 270 K. The heat capacity and entropy of this phase transition have been accounted for in terms of the Frenkel theory of heterophase fluctuation. Construction of an adiabatic-type calorimeter workable between 1.5 and 393 K has been also presented. 相似文献
10.
H.K. Sy 《Solid State Communications》1978,27(11):1127-1129
We investigate a model of two quasi-one-dimensional systems with electron and hole conductivity. We find that in general, Peierls ordering suppresses the possible excitonic pairing of the spatially separated electrons and holes. 相似文献