Discovery of Highly Excited Long-Lived Isomers in Neutron-Rich Hafnium and Tantalum Isotopes through Direct Mass Measurements

A study of cooled Au-197 projectile-fragmentation products has been performed with a storage ring. This has enabled metastable nuclear excitations with energies up to 3 MeV, and half-lives extending to minutes or longer, to be identified in the neutron-rich nuclides Hf-183,Hf-184,Hf-186 and Ta-186,Ta-187. The results support the prediction of a strongly favored isomer region near neutron number 116.

Molecular imprinting of nitrophenol and hydroxybenzoic acid isomers: effect of molecular structure and acidity on imprinting

Three nitrophenol isomer-imprinted polymers were prepared under the same conditions using 4-vinylpyridine as a functional monomer. Different recognition capacities for template molecules were observed for the three polymers. Another imprinting system with stronger acidity than nitrophenol isomers, 2-hydroxybenzoic acid (salicylic acid) and 4-hydroxybenzoic acid, was imprinted using 4-vinylpyridine or acrylamide as functional monomer respectively. Both 4-hydroxybenzoic acid-imprinted polymers using the two monomers showed recognition ability for the template molecule. However, when acrylamide was chosen as functional monomer, the salicylic acid-imprinted polymer showed very weak recognition for the template molecule, whereas strong recognition ability of the resultant polymer for salicylic acid was observed with 4-vinylpyridine as functional monomer. It seems that the structure and acidity of template molecules is responsible for the difference in recognition, by influencing the formation and strength of interaction between template molecule and functional monomer during the imprinting process. An understanding of the mechanism of molecular imprinting and molecular recognition of MIPs will help to predict the selectivity of MIPs on the basis of template molecule properties. Copyright (C) 2003 John Wiley Sons, Ltd.

Bonding and correlation analysis of various SiCO isomers

The structural properties for various SiCO isomers in the singlet and triplet states have been investigated using CASSCF methods with a 6-311 +G* basis set and also using three DFT and MP2 with same basis set for those systems except for the linear singlet state. The detailed bonding character is discussed, and the state-state correlations and the isomerization mechanism are also determined. Results indicate that there are four different isomers for each spin state, and for all isomers, the triplet state is more stable than the corresponding singlet state. The most stable is the linear SiCO ((3)Sigma(-)) species and may be refer-red to the ground state. At the CASSCF-MP2(full)/6-311+G* level, the state-state energy separations of the other triplet states relative to the ground state are 43.2 (cyclic), 45.2 (linear SiOC), and 75.6 kcal/mol (linear CSiO), respectively, whereas the triplet-singlet state excitation energies for each configuration are 17.3 (linear SiCO), 2.2 (cyclic SiCO), 10.2 (linear SiOC), and 18.5 kcal/mol (linear CSiO), respectively. SiCo ((3)Sigma(-)) may be classified as silene (carbonylsilene), and its COdelta- moiety possesses CO- property. The dissociation energy of the ground state is 42.5 kcal/mol at the CASSCF-MP2(full)/6-311+G* level and falls within a range of 36.5-41.5 kcal/mol at DFT level, and of 23.7-28.9 kcal/mol at the wave function-correlated level, whereas the vertical IP is 188.8 kcal/mol at the CASSCF-MP2(full)/6-311+G* level and is very close to the first IP of Si atom. Three linear isomers (SiCO, SiOC, and CSiO) have similar structural bonding character. SiOC may be referred to the iso-carbonyl Si instead of the aether compound, whereas the CSiO isomer may be considered as the combination of C (the analogue of Si) with SiO (the analogue of CO). The bonding is weak for all linear species, and the corresponding potential energy surfaces are flat, and thus these linear molecules are facile. Another important isomer is of cyclic structure, it may be considered as the combination of CO with Si by the side pi bond. This structure has the smallest triplet state-singlet state excitation energy (similar to2.2 kcal/mol); the C-O bonds are longer, and the corresponding vibrational frequencies are significantly smaller than those of the other linear species. This cyclic species is not classified as an epoxy compound. State-state correlation analysis and the isomerization pathway searches have indicated that there are no direct correlations among three linear structures for each spin state, but they may interchange by experiencing two transition states and one cyclic intermediate. The easiest pathway is to break the Si-O bond to go to the linear SiCO, but its inverse process is very difficult. The most difficult process is to break the C-O bond and to go to the linear CSiO.

Analysis of two trace alkaloid isomers in Strychnos nux-vomical by electrospray ionization tandem mass spectrometry

According to their molecular mass and ESI-MSn data, the trace alkaloid isomers pseudostrychnine and strychnine N-oxide in extracts of the total alkaloids from Strychnos nux-vomical were qualitatively analyzed by electrospray ionization tandem mass spectrometry (ESI-MSn) method after rough silica gel-column chromatographic separation. We also investigated the relationship between their fragmentation mechanism and structures of the two alkaloid isomers. A new method for quickly and highly sensitively analyzing the two alkaloid isomers was proposed.

Chromatographic separation and C-13 NMR characterization of aromatic diester-diacids isomers

Reverse phase high performance liquid chromatography (HPLC) was used to separate and quantify aromatic diester-diacids isomers which arise from the opening selectivity of anhydride rings towards methanol. C-13 NMR spectroscopy was a supplementary tool to characterize the isomer structure. It was found that a meta-position attack is slightly preferred in pyromellitic dianhydride (PMDA), while the preferred position of an attack in bridged dianhydrides is determined by the chemical nature (donors or accepters) of the bridged group. The stronger its electron-withdrawing abilities, the lower the probability of a meta-position attack.

FORMATION OF [C60C5H5] ADDUCT CATIONS AND THEORETICAL-STUDY OF THE ISOMERS

We study here the reactions between C-60 and planar C5H5+ cations that lead to the formation of [C60C5H5](+) adduct cations in the chemical ionization source of the mass spectrometer. The structures, stabilities and charge locations of some possible isomers of [C60C5H5](+): sigma-adduct, pi-complex, [1,4]- and [1,2]-addition cations, are studied by AM1 semiempirical molecular orbital calculations. We find that the most stable is the sigma-addition cation. Another interesting and stable structure is the pi-complex cation which is bonded by the electrostatic interaction at the inter-ring distance of 1.589 Angstrom with the C-5v symmetry. The C5H5+ cyclopentadienium cation seems to be an ''inverted umbrella'' sitting on a five-membered ring of the C-60 cage.

PRINCIPLES FOR STRUCTURE GENERATION OF ORGANIC ISOMERS FROM MOLECULAR FORMULA

An expert system for the elucidation of the structure of organic compounds (ESESOC) has been developed. The heart of the ESESOC is formed by the structure generator as an integral part, which receives the specific type of information (molecular formula, s

A STUDY OF CHARGE SEPARATION AND ELECTRON-CAPTURE INDUCED DECOMPOSITION SPECTRA OF PHENYLENEDIAMINE ISOMERS

The structures and decomposition reactions of doubly charged phenylenediamines were studied by means of charge separation (CS) and electron capture induced decomposition (ECID) spectra. The deisomerization of the three isomers is prior to the metastable d

A Study on the Unimolecular Decomposition of the Doubly Charged Ions Produced from 4 Chloro-toluene Isomers

The unimolecular charge separations and neutral loss decompositions of the doubly charged ions [C7H7Cl](2+), [C7H6Cl](2+) and [C7H5Cl](2+) produced in the ion source by 70 eV electron impact from 3 chloro-toluenes and benzyl chloride isomers were studied

A NEWLY PROPOSED MOLECULAR TOPOLOGICAL INDEX FOR THE DISCRIMINATION OF CIS/TRANS ISOMERS AND FOR THE STUDIES OF QSAR/QSPR

A new topological index, the general a(N)-index (GAI), on quantum chemistry, is described in this paper. The GAI can be applied to molecules that contain heteroatoms and multiple bonds, and performs well in distinguishing cis/trans isomers. The relationships between the GAIs and physicochemical properties of olefins and neutral phosphorus compounds were observed with satisfactory results.