Determination of rare and rare earth elements in soils and sediments by ICP-MS using Ti(OH)(4)-Fe(OH)(3) co-precipitation preconcentration

A method was developed for the determination of trace and ultratrace amounts of REE. Cd. In. Tl. Th. Nb, Ta. Zr and Hf in soils and sediments. With NaOH-Na2O2 as the flux. Ti(OH)(4)-Fe(OH)(3) co-precipitation as the preconcentration technique and inductively coupled plasma mass spectrometry (ICP-MS) for measurement, the whole procedure was concise and suitable for batch analysis of multi-element solutions. An investigation was carried out of the Ti(OH)(4)-Fe(OH)(3) co-precipitation system, and the results obtained showed that the natural situation of Ti tightly coexisting with Nb. Ta, Zr and Hf in geological samples plays a very important role in the complete co-precipitation of the four elements. The accuracy of this procedure was established using six Chinese soil and sediment certified reference materials (GSS and GSD). and the relative errors between the found and certified values were mostly below 10%.

Analysis of flavonoid constituents from leaves of Acanthopanax senticosus Harms by electrospray tandem mass spectrometry

Three known flavonoids, quercetin, quercitrin (quercetin-3-0-rhamnoside) and rutin (quercetin-3-0-rutinoside), have been identified for the first time in the leaves of Acanthopanax senticosus Harms by using electrospray tandem mass spectrometry techniques (ESI-MSn). The flavonoid hyperin (quercetin-3-0-beta-galactoside), already known to be present, was also investigated. The diagnostic fragment ions of the aglycone quercetin were obtained in the ESI-MSn experiments, and a fragmentation mechanism proposed.

Kinetics separation of copper and palladium by sodium hydroxide precipitation and its analytical application

The method of the kinetics separation of copper and palladium by sodium hydroxide precipitation was described. The reaction orders, apparent rate constants, apparent activation energy of the reactions between sodium hydroxide and copper, and palladium were determined, and the introduced error for the determination of palladium with separating copper and-palladium by sodium hydroxide precipitation was calculated, The proposed method has been applied to determine palladium in the aldehyde catalyst with good result.

Electrochemical and quartz crystal microbalance study for the electrochemical oxidation of 2-mercaptobenzimidazol

With the cyclic voltammetry and quartz crystal microbalance (QCM), the oxidation process and the electrodeposition behavior were studyied during the electrochemical oxidation of 2-mercaptobenzimidazol in aqueous solution. The E-pH diagram was also gained. These results showed the oxidation reaction was one electron reaction. The results from X-ray photoelectron spectrometry verified that the 2-mercaptobenzimidazol was oxidized to bisbenzimidazoyl disulfide.

Matrix effects in inductively coupled plasma mass spectrometry by use of organic solvents

Matrix effects arising from ethanol, propanol, glycerol, acetic acid, ethylenediamine and triethanolamine in inductively coupled plasma mass spectrometry have been studied. Addition of ethanol, propanol, glycerol, acetic acid, ethylenediamine and triethanolamine into solution has an enhancement effect on the signal intensity of analyte with ionization potential between 9 and 11 eV. The ethylenediamine and triethanolamine have higher enhancement effect on the signal intensity of Hg than that of ethanol, propanol, glycerol and acetic acid. Addition of ethylenediamine and triethanolamine into solution has a suppression effect on the signal intensity of Ph and Sr. The mechanism of the enhancement or suppression was investigated. The signal enhancement of Hg in the presence of ethylenediamine and triethanolamine is not caused by improved degree of ionization of Hg and nebulization efficiency. The suppression effects of Ph and Sr in the presence of ethylenediamine and triethanolamine are due to decrease of atomization efficiency of these elements. A method for the determination of Hg in the biological standard samples Ly ICP-MS was developed.

Identification of high-lying odd energy levels of uranium by resonant ionization mass spectrometry

Single-colour and two-colour multiphoton resonant ionization spectra of uranium atom were studied extensively with a Nd: YAG laser-pumped dye laser atomic beam apparatus time-of-flight mass spectrometer in our laboratory. The energy locations of high-lying odd-parity levels in the region 33 003-34 264 cm(-1),mearured by a two-colour three-step ionization technique, were reported here. The angular momentum quantum number J was uniquely assigned for these levels by using angular momentum selection rules.

Determination of ultra-trace rare-earth elements in human plasma by inductively coupled plasma mass spectrometry

Inductively coupled plasma mass spectrometry (ICP-MS),a highly sensitive inorgnic analytic technique,fits to determine ultra-nace rare-earth elements in human plasma. Under the optimized conditions detection limits for 15 rare-earth elements are in the range of 0.7 (for Eu)-5.4 (for Gd) ng.L-1. Indium as an internal standard element is used to compensate for matrix suppression effect and sensitivity drift. Three kinds of preparation methods, diluted with 1% HNO3, digested with HNO3-H2O2 and with HNO3-HClO4, are checked and compared,and the former is the simplest way to be measured. The samples diluted with 1% HNO3, stored in 4 degrees C, are very steady for 16 days. With the method, 11 healthy plasma samples in Changchun area of China are analysed.

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.

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.

Investigation of thermal unfolding process of cyanic adduct of horseradish peroxidase by Fourier transform infrared and circular dichroism spectrometry

Detailed circular dichroism(CD) and Fourier transform infrared (FTIR) studies have been carried out to monitor thermal unfolding of horseradish peroxidase isoenzyme C(HRP) inhibited by CN(HRP-CN). The results suggest that HRP-CN is quite different from native HRP with different spin states of Fe of heme and different coordinated states. Cyanide becomes the sixth ligand of Fe(I) of heme and the hydrogen-binding network is destroyed partly at the same time, which cause the drastic decrease of thermal stability of HRP. The FTIR and Soret-CD spectra analysis demonstrate that during the heating process there is an intermediate state(I') which has both partly destroyed secondary and tertiary structures of native HRP, then it is the appearance of protein aggregation state(A) after fully unfolding. The unfolding pathway thus can be shown as follows: I -->I'-->U -->A.

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.

Characteristics in frequency domain by inductively coupled plasma atomic emission spectrometry with charge injection detection

The charactesistics of two-dimension spectra obtained by inductively coupled plasma atomic emission spectrometry (ICP-AES) with charge injection detection (CID) in frequency domain were studied in the present paper. The measurement spectra were Fourier transformed and the frequency distribution of the spectra was obtained. Results showed that the spectra in frequency domain could he divided into two parts:high frequency and low frequency signals. The later stood for measurement spectra and the former for background and noises. However, the high frequecny signals could not be smoothed simply to reduce noises because the background was deteriorated even though the spectral signal did not change significantly.

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.

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%.