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Quan Xiang WE Xia LIU Yan Ping SHI 《中国化学快报》2005,16(11):1477-1480
A novel dimeric eremophilane, ligulolide B, was isolated from the alcoholic extract of the whole plant of Ligularia virgaurea spp. oligocephala. The structure was elucidated by various spectroscopic methods including intensive 2D NMR techniques (^1H-^1H COSY, gHMQC, gHMBC and ^1H-^1H NOESY) and HR-ESI-MS. 相似文献
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Burke RM Pearce JK Boxford WE Bruckmann A Dessent CE 《The journal of physical chemistry. A》2005,109(43):9775-9785
Multiply charged anions (MCAs) represent highly energetic species in the gas phase but can be stabilized through formation of molecular clusters with solvent molecules or counterions. We explore the intramolecular stabilization of excess negative charge in gas-phase MCAs by probing the intrinsic stability of the [adenosine 5'-triphosphate-2H](2-) ([ATP-2H](2-)), [adenosine 5'-diphosphate-2H](2-) ([ADP-2H](2-)), and H(3)P(3)O(10)(2-) dianions and their protonated monoanionic analogues. The relative activation barriers for decay of the dianions via electron detachment or ionic fragmentation are investigated using resonance excitation of ions isolated within a quadrupole trap. All of the dianions decayed via ionic fragmentation demonstrating that the repulsive Coulomb barriers (RCB) for ionic fragmentation lie below the RCBs for electron detachment. Both the electrospray ionization mass spectra (ESI-MS) and total fragmentation energies for [ATP-2H](2-), [ADP-2H](2-), and H(3)P(3)O(10)(2-) indicate that the multiply charged H(3)P(3)O(10)(2-) phosphate moiety is stabilized by the presence of the adenosine group and the stability of the dianions increases in the order H(3)P(3)O(10)(2-) < [ADP-2H](2-) < [ATP-2H](2-). Fully optimized, B3LYP/6-31+G* minimum energy structures illustrate that the excess charges in all of the phosphate anions are stabilized by intramolecular hydrogen bonding either within the phosphate chain or between the phosphate and the adenosine. We develop a model to illustrate that the relative magnitudes of the RCBs and hence the stability of these ions is dominated by the extent of intramolecular hydrogen bonding. 相似文献
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We report the first low-energy collisional excitation measurements and density functional theory calculations to characterize the ground state potential energy surfaces of contact ion-pair complexes that contain multiply charged anions (MCAs). Excitation of K+.Pt(CN)(4) (2-) and K+.Pt(CN)(6) (2-) result in fragmentation products associated with decay of the isolated constituent dianions, revealing that the ground state ion-pair surfaces are dominated by the intrinsic characteristics of the MCA. This observation is important since it indicates that counter-ion complexation only weakly perturbs the electronic structure of an MCA. For K+.Pt(CN)(4) (2-), where the Pt(CN)(4) (2-) dianion decays with production of two ionic fragments, we observe evidence for the existence of a novel exit-channel complex corresponding to a polar KCN salt unit bound to the Pt(CN)(3) (-) anion. The results described provide a basis for understanding the potential energy surfaces and fragmentation characteristics of other ion-pair complexes that involve MCAs. 相似文献
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Multiply charged anions (MCAs) represent exotic, highly energetic species in the gas-phase due to their propensity to undergo unimolecular decay via electron loss or ionic fragmentation. There is considerable fundamental interest in these systems since they display novel potential energy surfaces that are characterized by Coulomb barriers. Over recent years, considerable progress has been made in understanding the factors that affect the stability, decay pathways and reactivity of gas-phase MCAs, mainly as a result of the application of electrospray ionization as a generic technique for transferring solution-phase MCAs into the gas-phase for detailed characterization. We review contemporary work in this field, focusing on the factors that control the intrinsic stability of MCAs, both as isolated gas-phase ions, and on their complexation with solvent molecules and counter-ions. While studies of MCAs are primarily of fundamental interest, several classes of important biological ions are commonly observed as MCAs in the gas-phase (e.g. oligonucleotides, sugars). Recent results for biologically relevant ions are emphasised, since a fundamental understanding of the properties of gas-phase MCAs will be highly valuable for developing further analytical methods to study these important systems. 相似文献
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KM Clauwaert Van Bocxlaer JF HJ Major JA Claereboudt WE Lambert Van den Eeckhout EM Van Peteghem CH De Leenheer AP 《Rapid communications in mass spectrometry : RCM》1999,13(14):1540-1545
This paper describes the investigation of the potential of a quadrupole orthogonal acceleration time-of-flight mass spectrometer (Q-TOF) equipped with an atmospheric pressure ionisation interface for quantitative measurements of small molecules separated by reversed phase liquid chromatography. To this end, the detection limits and linear dynamic range in particular were studied in an LC/MS/MS experiment using 3,4-methylenedioxymethamphetamine standards and 3,4-methylenedioxyethylamphetamine for internal standardisation. In a second phase, the experiment was repeated with real biological extracts (whole blood, serum, and vitreous humour). A calibration for 3,4-methylenedioxymethamphetamine and its metabolite 3,4-methylenedioxyamphetamine was prepared in each of these matrices again using 3,4-methylenedioxyethylamphetamine as internal standard. The resulting quantitative data were compared with those obtained by liquid chromatography with fluorescence detection for the same extracts. The Q-TOF results revealed excellent sensitivity and a linear dynamic range of nearly four decades (2-10 000 pg on-column, r(2) = 0.9998, 1/x weighting). Furthermore, all the calibration curves prepared in biological material were superimposable, LC/MS/MS and LC-fluorescence, and the quantitative results for actual samples compared very favourably. It was concluded that the Q-TOF achieves a linear dynamic range for quantitative LC/MS/MS work exceeding that of fluorescence detection and at much better absolute sensitivity. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
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By means of a noncommutative differential calculus on function space of discrete Abelian groups and that of the regular lattice with equal spacing as well as the discrete symplectic geometry and a kind of classical mechanical systems with separable Hamiltonian of the type H(p, q) = T(p) + V(q) on regular lattice, we introduce the discrete symplectic algorithm, i.e., the phase-space discrete counterpart of the symplectic algorithm including original symplectic schemes and the jet-symplectic schemes in terms of the discrete time jet bundle formalism, on the regular lattice. We show some numerical calculation examples and compare the results of different schemes. 相似文献
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以香豆素为基用以识别氟离子的新型比色化学传感器 总被引:2,自引:1,他引:1
以香豆素作为发色团,胺基为氢键供体,以—C=N键桥连设计合成了可裸眼识别氟离子的化学传感器1,吸收光谱结果表明在乙腈中它可以高选择性识别氟离子,光谱红移70 nm,溶液颜色由橙色变为蓝紫色,而其它离子如Cl~-、Br~-、I~-、H_2PO_4~-、NO_3~-、HSO_4~-、AcO~-等均不影响其对氟离子的识别.通过核磁共振氢谱考察其识别机制,表明传感分子通过与F~-间的质子转移反应,使整个体系电子离域,分子内电荷转移更加显著,从而导致吸收光谱大幅红移. 相似文献