Rapid identification of saponins in plant extracts by electrospray ionization multi-stage tandem mass spectrometry and liquid chromatography/tandem mass spectrometry

Electrospray ionization multi-stage tandem mass spectrometry (ESI-MSn) and liquid chromatography coupled with on-line mass spectrometry (LC/MS/MS) were applied to characterize saponins in crude extracts from Panax ginseng. The MSn data of the [M - H](-) ions of saponins can provide structural information on the sugar sequences of the saccharide chains and on the sapogins of saponins. By ESI-MSn, non-isomeric saponins and isomeric saponins with different aglycones can be determined rapidly in plant extracts. LC/MS/MS is a good complementary analytical tool for determination of isomeric saponins. These approaches constitute powerful analytical tools far rapid screening and structural assignment of saponins in plant extracts. Copyright (C) 2000 John Wiley & Sons, Ltd.

Mass transfer of Er(III) between HBTMPTP dissolved in n-heptane and HAc-NaAc

The rate of extraction of Er(III) from aqueous acetate solutions at 0. 2 mol/L ionic strength by HBTMPTP in n-heptane was studied by using a constant interfacial area cell with laminar flow at (30+/- 0. 5)degrees C. The interfacial activity of HBTMPTP was investigated at n-heptane/0. 2 mol/L (H, Na)Ac (pH=5. 00) interface, The rate of Er(III) extraction was measured at different chemical compositions by varying hydrogen ion, HBTMPTP, Cyanex 302 and chlorine ion concentrations, The effect of stirring speed, temperature and special interfacial area on the rate of extraction was also studied. The results showed that, under the conditions of the experiments, the overall rate is diffusion controlled, that the impurities of Cyanex 302 have the effect of synergistic extraction.

Mass spectrometry study on snake venoms and enzymes

In this paper, three kinds of snake venoms and lour kinds of enzymes (phospholipase A(2), fibrinolytic enzyme, arginine esterase and L-amino acid oxidase) isolated from the snake venom were analyzed. As the snake venom was different, the MALDI/TOF/MS showed difference, The MALDI/TOF/MS determination results could be affected Ly the concentrations of snake venom enzymes, And the mechanisms of desorption and ionization was also given in this study, By using MALDI/TOF/MS we obtained the accurate molecular weights and homogeneities of the enzymes. The apparent characteristics of the positive MALDI/TOF/MS of enzymes composed by two subunits were also given out, The results showed that MALDI/TOF/MS is an effective analytic method for discovering new components from snake venom complexes. And it is reliable to use this method to determine the molecular weights and purifies of protein molecules.

Analysis of poly (arylene phosphonate) cyclic oligomer by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MAIDI-TOF-MS) was used for analysis of poly(arylene phosphonate) cyclic oligomers. A comparison was made by using 1,8,9-dithranol, 2,5-dihydroxybenzoic acid and retinoic acid as the matrix. The result showed that the retinoic acid produced the strongest ion signals under the conditions used. Different salts of metals were used as the cationization agents to examine the effect on the cyclic oligomers. It was found that the salts could produce metal-cyclic oligomer cation spectra and lithium was the stronger one than those of silver so, the suitable matrix and cationization agent for the new cyclic oligmer were obtained. They were very effective for the analysis of poly(arylene phosphonate) cyclic oligomer.

Use of nitrocellulose films for affinity-directed mass spectrometry for the analysis of antibody/antigen interactions

Combination of affinity extraction procedures with mass spectrometric analyses is termed affinity-directed mass spectrometry, a technique that has gained broad interest in immunology and is extended here with several improvements from methods used in previous studies. A monoclonal antibody was immobilized on a nitrocellulose (NC) membrane, allowing the corresponding antigen to be selectively captured from a complex solution for analysis by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). This method was also used to rapidly determine the approximate binding region responsible for the antibody/antigen interaction. The tryptic fragments of antigen protein in buffer were applied to the antibody immobilized on NC film and allowed to interact. The NC film was then washed to remove salts and other unbound components, and subjected to analysis by MALDI-TOFMS. Using interferon-alpha (2a) and anti-interferon-alpha (2a) monoclonal antibody IgG as a model system, we successfully extracted the antigen protein and determined the approximate binding region for the antigen/antibody interaction (i.e., the tryptic fragment responsible). Copyright (C) 2001 John Wiley & Sons, Ltd.

Gaseous dipeptide complexes with metal ions by electrospray ionization and tandem mass spectrometry

Electrospray ionization (ESI) and tandem mass spectrometry have been used to investigate the gas-phase interactions of five metal ions and seven dipeptides. For silver ion, two complexes ([M+Ag](+) and [2M+Ag](+)) were obtained as well as the one complex ([2M+Met-H](+)) for transition-metal ions. Upon collision activation, there is an obvious difference in MS/MS data between metal ion complex and the protonated molecule. The fragment pathway of each complex is related to the structures of dipeptide and the nature of metal ion which suggest that there are several interaction between the metal ions and dipeptides in gas phase.

Studies on negative electrospray ionization mass spectrometry on saponins

Two kinds of saponins have been investigated by negative electrospray ionization (NESI) mass spectrometry. Under ESI conditions, the [M - H](-) ions of saponins were observed which provide the molecular weights of saponins. The fragment pathways of [M - H](-) ions of these two saponins depend on their structures. For steroidic saponins, [M - H](-) ion only produces the fragment ions by the losses of sugar units. For oleanolic saponins, [M - H](-) ion yields the cross-ring ions as well as the fragment ions by the losses of sugar units. Moreover, the abundance of the former is higher than that of the latter. The characteristic fragments are used to provide the sequence and some linkage information of sugar moieties of saponins. Especially, their fragment difference strongly depends on the linkage between the aglycone and the sugar moieties.

Investigation of metalloporphyrins and their imidazole complexes using electrospray ionization mass spectrometry

Three compounds of metalloporphyrins were studied using electrospray ionization mass spectrometry. The bonding power between substitutional phenyl and porphyrin cycle and the coordinate conditions of metalloporphyrins with imidazole were discussed. The experimental result indicated that the bonding power between substitutional phenyl and porphyrin cycle in metalloporphyrins became weak from Mn, Fe to Co. The complexes abundances formed by metallophorphyrin with imidazole were stronger with the increase of the ligand concentration. At the same ligand concentration, the abundance of the complexes was intensified gradually and the stability of the ligands was become stronger from Mn, Fe to Co.

Application of inductively coupled plasma mass spectrometry in biological samples analysis

Recent important applications of inductively coupled plasma mass spectrometry in biological samples analysis are reviewed. The sample preparation, sample introduction techniques, interference correction and typical applications are introduced in detail with 154 references.

Preparation and mass spectrometric study of egg yolk antibody (IgY) against rabies virus

Rabies virus was used as the antigen to immunize laying chickens. Anti-rabies virus immunoglobulin Y(IgY) was isolated from yolks of the eggs laid by these chickens using a two-step salt precipitation and one-step gel filtration protocol. The purified IgY was reduced with dithiothreitol, and heavy chains (HC) and light chains (LC) were obtained. In addition, the purified IgY was digested with pepsin and the fragment with specific antigen binding properties (Fab) was produced. Using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-TOFMS), the average molecular weights of IgY, HC, LC, and Fab were determined as 167 250, 65 105, 18 660, and 45,359 Da, respectively. IgY has two structural differences compared with mammalian IgGs. First, the molecular weight of the heavy chain of IgY is larger than that of its mammalian counterpart, while the molecular weight of the light chain of IgY is smaller. Second, upon pepsin digestion, anti-rabies virus IgY is degraded into Feb, in contrast to mammalian IgG, which has been reported to be degraded into F(ab')(2) under the same conditions. Copyright (C) 2001 John Wiley & Sons, Ltd.

Metal ion adducts in the structural analysis of ginsenosides by electrospray ionization with multi-stage mass spectrometry

The effect of metal (Li+, Na+, K+, Ag+) cationization on collision-induced dissociation of ginsenosides was investigated by electrospray ionization mass spectrometry combined with multi-stage mass spectrometry (ESI-MSn). The fragments of sodiated and lithiated molecules give valuable structural information regarding the nature of the aglycone and the sequence and linkage information of sugar moieties. However, the number and relative abundances of fragment ions from lithiated ginsenosides are significantly greater than for the sodiated species, The K+ adducts undergo glycosidic cleavages and very limited cross-ring reactions. The silver ion adducts fragment mainly through glycosidic cleavages. Copyright (C) 2001 John Wiley & Sons, Ltd.

Mass spectrometric studies of metallofullerene

The endrohel metallofullerene, Gd@C-82, Gd@C-80, Gd-2@C-80 were synthesized by using K-H method. The technique of two-step of high pressure and high temperature extraction with 1, 3, 5-trimethylbenzene (first step) and pyridine(second step) has been successfully utilized to extract metallofullerene of Gd@C-82 The gas-phase negative ions of fullerenes C-n(n= 60, 70, 78, 82, 84...) and metallofullerene (Gd@C-82) have been studied by the ESI-MS, REC-MS and MALDI-TOF-MS. The differences among the mass spectra of ESI-MS, REC-MS and MALDI-TOF-MS have been observed and explained. In contrast to the empty fullerene C-82 , the metallofullerene Gd@C-82 should have a larger HOMO-LUMO gap. Experimental results suggest that Gd@C-82 is polarized and Gd3+ located in the off-center position of C-82 cage after Gd3+ is trapped into C-82 cage.

Studies on the nature of the macromolecular condensed state of "nascent" ultra high molar mass polyethylene

Ultra high molar mass polyethylene (UHPE) powder as polymerized in a slurry process has been studied, in its nascent state, after recrystallization on rapid cooling from the melt and after hot compression molding to a film, by DSC, effect of annealing the recrystallized specimen at 120 similar to 130 degreesC, morphology by polarizing optical microscopy and small angle X-ray scattering. Based on the experimental results obtained the macromolecular condensed state of the nascent UHPE powder is a rare case of a multi-chain condensed state of non-interpenetrating chains, involving interlaced extended chain crystalline layers and relaxed parallel chain amorphous layers. On melting, a nematic rubbery state of nanometer size domain resulted. The nematic-isotropic transition temperature was judged from literature data to be at least 220 degreesC, possibly higher than 300 degreesC, the exact temperature is however not sue because of chain degradation at such high temperatures. The recrystallization process from the melt is a crystallization from a nematic rubbery state. The drop of remelting peak temperature by 10 K of the specimen recrystallized from its melt as compared to the nascent state has its origin in the decrease both of the crystalline chain stem length and of the degree of crystallinity. The remelting peak temperature could be returned close to that of the nascent state by annealing at 120 similar to 130 degreesC.

Determination of the impurities elements in high-purity cadmium by inductively coupled plasma mass spectrometry

A method for the determination of impurity elements in high purity cadmium by inductively coupled plasma mass spectrometry was developed. The spectral interference arising from Cd was discussed and the magnitude of interference by the polyatomic ion of Cd was compared. The effect of the high concentration Cd on the analyte signal was studied. The results showed that Cd possessed both significant suppression effects on the light mass elements signal and enhancement effects on the heavy mass elements signal,and the effects can be corrected by the use of internal standard elements. In this paper, Y and Bi was employed for the light mass elements and the heavy mass elements,respectively. As, Be, Co, Cu, Ga, Ge, Mn, Mo, Pb, Ni, Sr, Au, Tl, Th, V and U in high purity cadmium were determined. Detection limits are 0.005-0.052 mu g L-1,and the recoveries of standard addition are 82%-108%.

Investigation of a series of synthetic cationic porphyrins using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) was used to study a series of synthetic cationic porphyrins as the perchlorate and bromide salts. This work presents the analytical results for the porphyrins obtained using 2,5-dihydroxybenzoic acid (DHB) and 1,8,9-anthratriol as matrices. The selective use of matrix affects ion formation from these porphyrins. By using DHB as the matrix, we not only observed [M - nCIO(4)](+) (n = 1-4) ions, but also obtained [2M - nCIO(4)](+) (n = 2-7) ions from the synthetic cationic porphyrins. The space volume of the side chains (R groups) and the nature of the anions (Br- or CIO4-) affected the relative importance of monomeric and dimeric ions of the porphyrin. The possible mechanisms of desorption and ionization of these cationic porphyrins were also considered in this study. MALDI-TOFMS proved to be a very useful method for obtaining structural information on these synthetic cationic porphyrins. Copyright (C) 1999 John Whey & Sons, Ltd.