Mass spectrometry study combined with theoretical calculation on the unimolecular fragmentation of tetrahydroimidazole-substituted methylene beta-diketones

Studies of low-energy collision-induced dissociation and isotopic labeling on ionized tetrahydroimidazole-substituted methylene P-diketones by tandem mass spectrometry showed that their unimolecular fragmentations may involve the reactions of intermediate ion/neutral complexes and multistep rearrangements. The corresponding mechanisms were proved by semiemipirical calculations of PM3 and AM1 methods.

Sites of protonation and unimolecular fragmentation of protonated N-hydroxyphthalimide in the gas phase

The low energy collision-induced dissociation, linked scan techniques and isotopic labeling experiment were used to investigate the unimolecular fragmentation of protonated N-hydroxyphthalimide under electron impact and chemical ionization conditions. It was found that this compound shows an unusual reactivity towards protonation. Two possible sites of protonation have been proposed to explain the corresponding fragmentation processes, one is that the protonation takes place on the oxygen atom of hydroxyl group, resulting in the loss of water and the other is the formation of an intermediary proton-bound complex in the fragmentation process, giving rise to the fragment ions of m/z 133 and m/z 135. The results show both cases are coexistence in the fragmentations of protonated N-hydroxyphthalimide, and the unimolecular fragmentation pathways are available.

Ion/neutral complex-mediated reactions generated from some ionized tetrahydroimidazole-substituted methylene beta-diketones

The dissociation of gaseous metastable ions of m/z 153 and the formation of ions of m/z 139 from the unimolecular fragmentations of ionized tetrahydroimidazole-substituted methylene beta-diketones were examined by tandem mass spectrometry. In addition, some other fragments accompanying the elimination of either an H2O molecule or an CHO. radical were also observed in the collision-induced dissociation spectra of molecular ions of the compounds bearing an aromatic ring. Collision-induced dissociation and isotopic labeling showed that these processes may involve reactions of intermediate ion/neutral complexes and multistep rearrangements. The corresponding mechanisms are discussed. (C) 1997 by John Wiley & Sons, Ltd.

Investigation of "Rearrangement Step" in classical Beckmann rearrangement mechanism over solid acid by means of O-18 isotopic

The reaction mechanism of the Beckmann rearrangement over B2O3/gamma-Al2O3 and TS-1 in the gas phase has been investigated by isotope labeling approach. The isotopic labeled products were measured by mass spectrometry method. By exchanging oxygen with H, 180 in the rearrangement step, it was found that the exchange reaction between cyclohexanone oxime and (H2O)-O-18 over B2O3/-gamma-Al2O3 and TS-1 could only be carried out in some extent. It suggested that the dissociation of nitrilium, over solid acids be not completely free as the classical mechanism. A concept of the dissociation degree (alpha) that is defined as the ratio of the dissociated intermediate nitrilium to the total intermediate nitrilium has been proposed. By fitting the experimental values with the calculation equation of isotopic labeled products, it is obtained that a values for B2O3/-gamma-Al2O3 and TS-1 are 0.199 and 0.806 at the reaction conditions, respectively.

Ablation of hydrogen isotopic spherical pellet due to the impact of energetic ions of the respective isotopes

The ablation rate of a hydrogen isotopic spherical pellet G(is) due to the impact of energetic ions of the respective isotopes and its scaling law are obtained using the transsonic neutral-shielding model, where subscript s might refer to either hydrogen or deuterium. Numerical results show that if E0s/E0e2 greater-than-or-equal-to 1.5, G(is)/G(es) greater-than-or-equal-to 20%, where E0s and E0e are the energy of undisturbed ion and electron, respectively, and G(es) is the ablation rate of a pellet due to the impact of electrons. Hence, under the NBI heating, the effect of the impact of energetic ions on the pellet ablation should be taken into consideration. This result also gives an explanation of the observed enhancement of pellet ablation during NBIH.

Diel isotopic fluctuation in surface seston and its physiological and ecological implications

We reported diet fluctuation in isotopic composition of surface seston from two connected lakes in China, oligotrophic Lake Fuxian and eutrophic Lake Xingyun. The decrease in nighttime and the increase in daytime of isotope signatures of seston might be attributed to the light-dependent balance between the photosynthesis and the respiration of phytoplankton and to the changes in the species composition and the relative abundance of phytoplankton functional groups at the water's surface in diel growth. The relatively high isotopic signatures and the large-extent diel fluctuation of phytoplankton in the eutrophic lake could be due to utilization of heavy-isotope-enriched inorganic sources and the high primary productivity. Extent of diel fluctuation in delta C-13 and delta N-15 of phytoplankton were relatively small compared with the isotopic enrichment per trophic transfer and thus might have negligible effect on the source identification and the trophic evaluation of consumers.

Application of methyl parathion hydrolase (MPH) as a labeling enzyme

Methyl parathion hydrolase (MPH) is an enzyme that catalyzes the degradation of methyl parathion, generating a yellow product with specific absorption at 405 nm. The application of MPH as a new labeling enzyme was illustrated in this study. The key advantages of using MPH as a labeling enzyme are as follows: (1) unlike alkaline phosphatase (AP), horseradish peroxidase (HRP), and glucose oxidase (GOD), MPH is rarely found in animal cells, and it therefore produces less background noise; (2) its active form in solution is the monomer, with a molecular weight of 37 kDa; (3) its turnover number is 114.70 +/- 13.19 s(-1), which is sufficiently high to yield a significant signal for sensitive detection; and (4) its 3D structure is known and its C-terminal that is exposed to the surface can be easily subjected to the construction of genetic engineering monocloning antibody-enzyme fusion for enzyme-linked immunosorbent assay (ELISA). To demonstrate its utility, MPH was ligated to an single-chain variable fragment (scFv), known as A1E, against a white spot syndrome virus (WSSV) with the insertion of a [-(Gly-Ser)(5)-] linker peptide. The resulting fusion protein MPH-A1E possessed both the binding specificity of the scFv segment and the catalytic activity of the MPH segment. When MPH-A1E was used as an ELISA reagent, 25 ng purified WSSV was detected; this was similar to the detection sensitivity obtained using A1E scFv and the HRP/Anti-E Tag Conjugate protocol. The fusion protein also recognized the WSSV in 1 mu L hemolymph from an infected shrimp and differentiated it from a healthy shrimp.