Your browser doesn't support javascript.
loading
Show: 20 | 50 | 100
Results 1 - 10 de 10
Filter
Add more filters










Publication year range
1.
Article in English | MEDLINE | ID: mdl-17881784

ABSTRACT

Chemical ionization of a mixture of nitrogen and carbon monoxide produces three stable isobaric species at m/z 56: OCCO, OCNN and NNNN radical cations. Separated at increased resolution, these ions are readily identified by collisional activation. Neutralization-reionization experiments performed on two different mass spectrometers have not allowed the detection of any recovery signals for the corresponding neutrals.

2.
Sci Total Environ ; 356(1-3): 275-89, 2006 Mar 01.
Article in English | MEDLINE | ID: mdl-16055170

ABSTRACT

Sea stars (Asterias rubens L.) were collected in different stations distributed in the Southern Bight of the North Sea. Concentrations of four heavy metals and six PCB congeners were measured in two body compartments (body wall and pyloric caeca). In order to assess the potential harm of these contaminants, two biochemical parameters were measured in sea stars, viz. reactive oxygen species (ROS) production by amoebocytes and cytochrome P450 immunopositive protein (CYP1A IPP) induction in pyloric caeca. Sea stars from stations located in the plume of the Scheldt river showed the highest contamination levels. Other stations, similarly located, displayed lower levels. No simple relationship could be established between ROS production by sea star amoebocytes and contaminant levels measured in sea star tissues. CYP1A IPP induction displayed more contrasted responses, and highly significant regressions were found between PCB concentrations measured in pyloric caeca and CYP1A IPP. Both biological parameters were found to vary significantly over the study area. On the whole, data indicated that contamination levels and subsequent effects in sea stars were comparable to those described in previous large-scale studies, but that working at a smaller scale highlighted the existence of patterns of contamination which can blur general trends due to major contamination sources like contaminated rivers.


Subject(s)
Asterias , Metals, Heavy , Polychlorinated Biphenyls , Water Pollutants, Chemical/analysis , Animals , Asterias/drug effects , Asterias/growth & development , Asterias/metabolism , Metals, Heavy/analysis , Metals, Heavy/pharmacokinetics , Metals, Heavy/toxicity , North Sea , Polychlorinated Biphenyls/analysis , Polychlorinated Biphenyls/pharmacokinetics , Polychlorinated Biphenyls/toxicity , Water Pollutants, Chemical/pharmacokinetics , Water Pollutants, Chemical/toxicity
3.
Rapid Commun Mass Spectrom ; 20(2): 151-6, 2006.
Article in English | MEDLINE | ID: mdl-16331727

ABSTRACT

Dissociative ionization of the selenourea Se=C(NH(2))(2) (2) conveniently generates beams of pure isocyanoselenic acid radical cations. The HNCSe(.+) connectivity is established by collisional activation and by associative ion-molecule reactions with dimethyl sulfide or nitric oxide using a large-scale hybrid mass spectrometer.


Subject(s)
Mass Spectrometry/methods , Microchemistry/methods , Organoselenium Compounds/analysis , Organoselenium Compounds/chemistry , Urea/analogs & derivatives , Cations , Free Radicals/analysis , Free Radicals/chemistry , Isomerism , Reproducibility of Results , Sensitivity and Specificity , Urea/analysis , Urea/chemistry
4.
Sci Total Environ ; 333(1-3): 149-65, 2004 Oct 15.
Article in English | MEDLINE | ID: mdl-15364526

ABSTRACT

The Southern Bight of the North Sea is particularly exposed to anthropogenic contamination, due to heavy urbanisation and industrialisation of its catchment area. The present work focuses on polychlorinated biphenyl (PCB) and metal contamination of the marine environment along and off the Belgian coast. Its objectives were to compare the concentrations of seven PCB congeners and four heavy metals in the sediments (a repository for anthropogenic contaminants) and in the asteroid Asterias rubens (a recognized bioindicator species). Nineteen sampling stations were considered between the mouth of the Scheldt Estuary and the southern limit of the Belgian coast (asteroids were found in 10 out of the 19 stations). PCB and metal concentrations measured in sediments and asteroids were in the range of values reported in previous studies. Stations under direct influence of the Scheldt were the most impacted by the considered contaminants. Metal concentrations varied according to the grain-size fraction considered. In asteroids, PCBs and metals were found to be selectively distributed among body compartments, and pyloric caeca were found to most efficiently discriminate between sampling stations contamination levels. PCB and metal analysis of sediments provided a physicochemical evaluation of the contamination, whereas analysis of asteroids introduced a biological dimension to the approach by taking into account bioavailability of the contaminants.


Subject(s)
Environmental Pollutants/analysis , Geologic Sediments/chemistry , Metals, Heavy/analysis , Polychlorinated Biphenyls/analysis , Starfish/chemistry , Animals , Environmental Monitoring , Environmental Pollutants/pharmacokinetics , Metals, Heavy/pharmacokinetics , North Sea , Polychlorinated Biphenyls/pharmacokinetics , Tissue Distribution
5.
J Org Chem ; 66(5): 1827-31, 2001 Mar 09.
Article in English | MEDLINE | ID: mdl-11262134

ABSTRACT

Aryliminopropadienethiones 9 have been generated by flash vacuum thermolysis of isoxazolones of the type 5 and characterized by mass spectrometry and matrix isolation IR spectroscopy in conjunction with DFT calculations and chemical trapping.

6.
J Mass Spectrom ; 36(1): 97-101, 2001 Jan.
Article in English | MEDLINE | ID: mdl-11180650

ABSTRACT

Collisional activation of keV thiophene-2-one radical cations 1(+*) with O(2) or NO(*) as the target gas leads to a desulfuration reaction. This peculiar reaction is insignificant or absent with other targets such as helium, argon, methane or nitrogen. The radical cations produced in this desulfuration reaction are most probably vinylketene ions, as indicated by a triple mass spectrometric (MS/MS/MS) experiment performed on a 'hybrid' tandem mass spectrometer of sector--quadrupole--sector configuration. Tentatively, it is proposed that population of an excited state accounts for the non-ergodic behavior of 1(+*) upon collision with oxygen or nitric oxide. Ab initio molecular orbital calculations using molecular orbital theory (UMP2, UCCSD(T)) and density functional theory (B3LYP) with 6--31G(d,p) and 6--311++G(d,p) basis sets were used to evaluate the relative energy of the excited quartet state of 1(+*) radical cations. This quartet state is calculated to lie about 3.6 eV above the (2)A(") ground state and 0.9 eV above the C(4)H(4)O(+*)+S dissociation products. It is proposed that the quartet ion serves as the precursor for the spontaneous desulfuration.

7.
J Org Chem ; 65(9): 2706-10, 2000 May 09.
Article in English | MEDLINE | ID: mdl-10808443

ABSTRACT

Flash vacuum thermolysis (FVT) of 6-aryl-1,3-dioxine-4-thiones 9 leads to the formation of acylthioketenes 10, which are characterized by Ar matrix IR spectroscopy as well as on-line tandem mass spectrometry. The thioketenes 10 undergo a 1,3-shift of the aryl group to generate thioacylketenes 11. Ketenes 11 cyclize to 3-aryl-thiet-2-ones 12, which are also characterized by matrix IR spectroscopy and tandem mass spectrometry. The thiet-2-ones 12 undergo two kinds of reaction under the FVT conditions: (i) cheletropic CO extrusion with formation of arylthioketenes 13, and (ii) cycloreversion to COS and arylacetylene.

8.
Mass Spectrom Rev ; 19(6): 367-89, 2000.
Article in English | MEDLINE | ID: mdl-11199377

ABSTRACT

This review will be concerned with the gas phase chemistry of 1,2- and 1,3-dipolar systems that contain a carbon-nitrogen bond. Although most of these compounds are stable molecules under normal conditions, certain congeners are reactive species that cannot be prepared using conventional procedures. The isolation and observation of these elusive compounds therefore require appropriate experimental conditions such as those provided by the gas phase of a mass spectrometer. In these experiments, the radical cations, corresponding to the molecule under study, must be prepared via indirect procedures, including dissociative electron ionization, on-line flash-vacuum pyrolysis-mass spectrometry, or ion-molecule reactions. Their characterization is mainly based on collisional activation and ion-molecule reactions. The formation of the corresponding highly reactive neutrals is attempted by neutralization-reionization mass spectrometry. This review presents more than one hundred different molecules together with their methods of preparation and the experiment used to identify them.

9.
Rapid Commun Mass Spectrom ; 13(17): 1707-11, 1999.
Article in English | MEDLINE | ID: mdl-10455238

ABSTRACT

1,2-Hydrogen shift isomers of ionized pyridine, thiazole and imidazole are readily characterized by the study of their associative ion-molecule reactions with dimethyl disulfide in the quadrupole collision cell of a new hybrid sector-quadrupole-sector mass spectrometer. Efficient trapping reactions of CH(3)S(.) radicals are indeed observed and the actual structure of the adduct [M + CH(3)S](+) ions is clearly indicated by their high-energy collisional activation mass spectra. These trapping reactions are not observed for the 'conventional' pyridine, thiazole and imidazole molecular ions, which only react by charge exchange producing m/z 94, [CH(3)SSCH(3)](*+), ions.


Subject(s)
Heterocyclic Compounds/chemistry , Free Radicals/chemistry , Imidazoles/chemistry , Mass Spectrometry , Pyridines/chemistry , Thiazoles/chemistry
10.
Steroids ; 31(1): 31-48, 1978 Jan.
Article in English | MEDLINE | ID: mdl-26993

ABSTRACT

Mass-analyzed ion kinetic energy spectrometry (MIKE) is shown to be an efficient and rapid method for the analysis of complex sterol mixtures. The method has been applied to the study of the free sterol fractions of five marine and one freshwater invertebrates.


Subject(s)
Cnidaria/analysis , Porifera/analysis , Sterols/analysis , Animals , Mass Spectrometry/methods
SELECTION OF CITATIONS
SEARCH DETAIL
...