Importance of self-consistency in relativistic continuum random-phase approximation calculations

A fully consistent relativistic continuum random phase approximation (RCRPA) is constructed, where the contribution of the continuum spectrum to nuclear excitations is treated exactly by the single-particle Green's function technique. The full consistency of the calculations is achieved that the same effective Lagrangian is adopted for the ground state and the excited states. The negative energy states in the Dirac sea are also included in the single-particle Green's function in the no-sea approximation. The currents from the vector meson and photon exchanges and the Coulomb interaction in RCRPA are treated exactly. The spin-orbit interaction is included naturally in the relativistic frame. Numerical results of the RCRPA are checked with the constrained relativistic mean-field theory. We study the effects of the inconsistency, particularly the currents and Coulomb interaction in various collective multipole excitations.

Characterization of saccharides and phenolic acids in the Chinese herb Tanshen by ESI-FT-ICR-MS and HPLC

This study sought to determine the main components (saccharides and phenolic acids) in crude extract of the Chinese herb Tanshen by electrospray ionization Fourier transform ion cyclotron resonant mass spectrometry (ESI-FT-ICR-MS) in negative-ion mode. Eleven compounds were identified as phenolic acids by exact mass measurement and further confirmed by sustained off-resonance irradiation (SORI) CID data. In addition, monosaccharicles and oligosaccharides (n = 2 similar to 5) and a serial of corresponding anionic adducts of saccharide were observed without adding any anions additionally to the extract solution, and the anionic components were unambiguously identified as H2O, HCl, HCOOH, HNO3, C3H6O2, H2SO4 and C5H7NO3 according to the exact mass measurement results.

Evaluation of flavonoids binding to DNA duplexes by electrospray ionization mass spectrometry

In this study, electrospray ionization mass spectrometry (ESI-MS) was used to investigate the binding interactions of ten flavonoid aglycones and ten flavonoid glycosides with DNA duplexes. Relative binding affinities of the flavonoids toward DNA duplexes were estimated based on the fraction of bound DNA. The results revealed that the 4'-OH group of flavonoid aglycones was essential for their DNA-binding properties. Flavonoid glycosides with sugar chain linked on ring A or ring B showed enhanced binding toward the duplexes over their aglycone counterparts, whereas glycosylation of the flavonol quercetin on ring C exhibited a less pronounced effect.

Studies on the components of crude and processed Fructus Corni by ESI-MSn

The components of crude and processed Fructus Corni were investigated by means of electrospray ionization-tandem mass spectrometry(ESI-MSn) technique in the negative ion mode. Compared with those of crude Fructus Corni, the chemical components of the processed Fructus Corni were changed both in quality and in quantity. From the ESI-MS spectra of the crude and processed Fructus Corni, six peaks were selected to establish the characteristic ESI-MS peaks. Several factors in the processing procedure were examined.

Studies on the Biotransformation of Arctigenin Using Electrospray Ionization Mass Spectrometry

To study the biotransformation of arctigenin, arctigenin was anaerobically incubated with Eubacterium sp. ARC-2 of human intestinal bacteria in vitro. Arctigenin formed a molecular ion [M-H](-) in negative ion mode. The arctigenin and its metabolites were investigated directly by the electrospray ionization tandem mass spectrometry ion trap and Fourier transform ion cyclotron resonance. Arctigenin was transformed to 4',4 ''-dihydroxylenterolactone by E sp. ARC-2 through 3 types of demethylation products.

Identification of Phenylethanoid Glycosides in Plant Extract of Plantago asiatica L. by Liquid Chromatography-Electrospray Ionization Mass Spectrometry

The present work describes a liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) method for rapid identification of phenylethanoid glycosides in plant extract from Plantago asiatica L. By using a binary mobile phase system consisting of 0.2% acetic acid and acetonitrile under gradient conditions, a good separation was achieved on a reversed-phase C-18 column. The [M-H](-) ions, the molecular weights, and the fragment ions of phenylethanoid glycosides were obtained in the negative ion mode using LC-ESI-MS. The identification of the phenylethanoid glycosides (peaks 1-3) in the extract of P. asiatica L. was based on matching their retention time, the detection of molecular ions, and the fragment ions obtained by collision-induced dissociation (CID) experiments with those of the authentic standards and data reported in the literature.

Analysis on Iridoid Glycosides in Crude and Processed Extracts from Cornus Officinals by Liquid Chromatography-electrospray Ionization Mass Spectrometry

The iridoid glycosides in crude and processed extracts from cornus officinals have been analyzed by high performance liquid chromatography-electrospray ionization mass spectrometry. Samples were analyzed by a reversed-phase C18 column using a binary eluent under gradient conditions. Seven iridoid glycosides could be separated and detected. The [M-H](-) ions of iridoid glycosides in the negative ion mode were observed, which reflect their molecule mass information. An in-source collision induced dissociation (in-source CID) experiment was carried out in order to identify the structures and to measure the contents of iridoid glycosides. The epimers were discovered in the experiment for the first time, namely 7 alpha-O-ethyl-morroniside and 7 beta-O-ethylmorroniside.

Investigation of heptakis(2,6-di-O-methyl)-beta-cyclodextrin inclusion complexes with flavonoid glycosides by electrospray ionization mass spectrometry

The non-covalent complexes between three flavonoid glycosides (quercitrin, hyperoside and rutin) and heptakis(2,6-di-O-methyl)-beta-cyclodextrin (DM-beta-CD) were investigated by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS). The 1:1 complexation of each flavonoid glycoside (guest) to the DM-beta-CD (host) was monitored in the negative ion mode by mixing each guest with an up to 30-fold molar excess of the host. The binding constants for all complexes were calculated by a linear equation in the order: DM-beta-CD:quercitrin > DM-beta-CD:rutin > DM-beta-CD:hyperoside. A binding model for the complexes has also been proposed based on the binding constants and tandem mass spectrometric data of these complexes.

Studies on the doubly charged cluster ions of sodium and potassium nitrates by electrospray ionization tandem mass spectrometry

Doubly charged cluster ions, besides singly charged cluster ions, from sodium and potassium nitrates were produced evidently under normal source capillary temperature of 200 degrees C in both positive and negative ion electrospray ionization (ESI) ion trap mass spectrometry. The fragmentation pathways for doubly charged cluster ions were studied in detail using ESI tandem mass spectrometry and two pathways were observed depending on the cluster sizes of alkali metal nitrates. In addition, factors that affect the formation of cluster ions were also interrogated.

两种黄酮醇苷同分异构体的电喷雾质谱区分

Two flavonol glycoside isomers of Icariside Ⅰ and Caohuoside C were differentiated by electrospray ionization tandem mass spectrometry (ESI-MSn) method.In the negative ion mode,the two compounds with different glycosyl moieties showed the same ESI-MS spectrum,but obvious different MS2 spectra and thus they can be distinguished rapidly,accurately and easily by ESI-MS.

Structural analysis of selected characteristic flavones by electrospray tandem mass spectrometry

Seven structure analogical flavonoid aglycones have been analyzed using electrospray ionization tandem mass spectrometry (ESI-MSn) in the negative-ion mode. The spectra obtained ESI-MSn allowed us to propose plausible schemes for their fragmentation mechanism. By analyzing the product ions spectra of deprotonated molecule ions [M-H](-), some neutral diagnostic losses and specific retro Diels-Alder fragments were obtained. By using all of these characteristic fragment ions we can specially differentiate the flavone isomer.

Characterization of non-covalent complexes of rutin with cyclodextrins by electrospray ionization tandem mass spectrometry

Electrospray ionization tandem mass spectrometry (ESI-MSn) and the phase solubility method were used to characterize the gas-phase and solution-phase non-covalent complexes between rutin (R) and alpha-, beta- and gamma-cyclodextrins (CDs). The direct correlation between mass spectrometric results and solution-phase behavior is thus revealed. The order of the 1:1 association constants (K-c) of the complexes between R and the three CDs in solution calculated from solubility diagrams is in good agreement with the order of their relative peak intensities and relative collision-induced dissociation (CID) energies of the complexes under the same ESI-MSn condition in both the positive and negative ion modes. Not only the binding stoichiometry but also the relative stabilities and even binding sites of the CD-R complexes can be elucidated by ESI-MSn. The diagnostic fragmentation of CD-R complexes, with a significant contribution of covalent fragmentation of rutin leaving the quercetin (Q) moiety attached to the CDs, provides convincing evidence for the formation of inclusion complexes between R and CDs. The diagnostic fragment ions can be partly confirmed by the complexes between Q and CDs. The gas-phase stability order of the deprotonated CD-R complexes is beta-CD-R > alpha-CD-R > gamma-CD/R; beta-CD seems to bind R more strongly than the other CDs.

Identification of the flavonoid constituents from leaves of Acanthopanax Senticosus Harms

Four flavonoids from leaves of Acanthopanax Senticosus Harms were observed in negative ion mode in the electrospray mass spectra. Two of them were further isolated and identified as quercitrin (quercetin-3-O-alpha-L-rhamnoside) and hyperin (quercetin-3-O-beta-D-galactoside) on the basis of MS' and NMR data. The other two compounds in the mixtures were tentatively established as quercetin and rutin (quercetin-3-O-rutinoside) in terms of their electrospray tandem mass spectrometry (ESI-MSn) data. Three of the four flavonoids (excluding hyperin) haven't been reported in this plant before.

Study on new typical ionic clusters K+ (KNO3)(n) and NO3-(KNO3)(m)

The sample solution of KNO3 is ejected into the gas phase and the ionic dusters of K+(KNO3)(n) and NO3-(KNO3)(m) we formed and observed by electrospray ionization mass spectrometry (ESIMS). The full mass spectra of both the positive ion and the negative ion show that the differences between each peak nearby are all about 101(m/z), which correspond to the molecular weight of KNO3. The general formula of the ionic clusters can be assigned as K+ (KNO3)(n) and NO3--(KNO3)(m).

New typical ionic cluster K+(KNO3)(n) and NO3-(KNO3)(m)

New typical ionic clusters with complex anions could be formed directly from the KNO3 aqueous solution by means of the electrospray ionization mass spectrometry(ESIMS). The difference between the neighboring peaks(m/z), which corresponded to the molecule weight of KNO3 being 101 in the full mass spectrometry of the positive-ion and the negative-ion. The general formula of the ionic clusters belonged to K+(KNO3)(n) and NO3- (KNO3)(m).