Gas-phase ion-molecule reactions of neutral C-60 with alkyl methyl ethers under chemical ionization conditions

Gas-phase ion-molecule reactions of buckminsterfullerene (C-60) with the ion systems generated from the self-chemical ionization of alkyl methyl ethers (CH3OR, R = n-C2H5, n-C3H7, n-C4H9) were studied in the ion source of a mass spectrometer. The adduct cation [C60C2H5O](+) and protonated molecule [C60H](+) were observed as the major products. The former adduct ion was produced by the reactions of C-60 with the methoxymethyl ion [CH3OCH2](+), and the latter resulted from the proton transfer reactions from protonated alkyl methyl ethers to C-60 It is suggested that the [3+2] cycloadduct to a 6-6 bond of C-60 (a C-C bond common to two annulated six-membered rings) is the most favorable structure among the probable isomers of [C60C2H5O](+). (C) 1998 John Wiley & Sons, Ltd.

Gas phase derivations of endohedral metallofullerenes by ion-molecular reactions

Gas phase ion-molecular reactions of endohedral metallofullerenes with the self-chemical ionization ion system of vinyl acetate, benzene and acetone in the ion source of the mass spectrometer have been studied. Several derivatized endohedral metallofullerene cations [M@C-82-C2H3O](+), [M-2@C-80-C2H3O](+), [M@C-82-C6H6](+) and [M@C-82-CO-CH3](+) are observed as the major products. The experimental results indicate that endohedral metallofullerenes have active gas phase reactivities and can be efficiently derivatized by some small organic cations.

Gas-phase ion-molecule reactions of C-60 and theoretical studies of [C60C2H3O](+) adduct cations

Gas-phase ion-molecule reactions of buckminsterfullerene (C-60) with the acetyl cation CH3-C-+=O (m/z 43) and formylmethyl cation (CH2)-C-+-CH=O (m/z 43, or oxiranyl cation), generated from the self-chemical ionization of acetone and vinyl acetate, respectively, were studied in the ion source of a mass spectrometer. Adduct cations [C60C2H3O](+) (m/z 763) and protonated C-60, [C60H](+) (m/z 721), were observed as the major products. AM1 semiempirical molecular orbital calculations on the possible structures, stabilities and charge locations of the isomers of the adducts [C60C2H3O](+) were carried out at the restricted Hartree-Fock level. The results indicated that the sigma-addition product [C-60-COCH3](+) is the most stable adduct for the reaction of C-60 with CH3-C-+=O rather than that resulting from the [2+2] cycloaddition. The [2+3] cycloadduct and the sigma-adduct [C60CH2CHO](+) might be the most possible coexisting products for the reactions of C-60 with (CH2)-C-+-CH=O or oxiranyl cation. Other [C60C2H3O](+) isomers are also discussed. (C) 1997 by John Wiley & Sons, Ltd.

Compatibility and specific interactions in poly(beta-hydroxybutyrate) and poly(p-vinylphenol) blends

The miscibility and specific interactions in poly (beta-hydroxybutyrate) (PHB)/poly(p-vinylphenol) (PVPh) blends were studied by differential scanning calorimetry(DSC) , fourier transform infrared(FTIR) spectrometer and high resolution solid state C-13 NMR, A single composition-dependent glass transition temperatures were obtained by DSC which indicate the blends of PHB/PVPh were miscible in the melt state, The experimental glass transition temperatures were fitted quite well with those obtained from Couchman-Karasz equation. The FTIR study shows that the strong intermolecular hydrogen bonding exists in blends of PHB with strong proton acceptor and PVPh with strong proton donor and is the origin of its compatibility. The CPMAS C-13 NMR spectra also show that the strong hydrogen bonding exists in PHB/PVPh blends. From the T-1 rho(H) relaxation time it follows that the blends of PHB/PVPh(40/60, 20/80) studied are completely homogeneous on the scale of about 3.2 nm.

Effects of zeolites on the pyrolysis of polypropylene

With the intention of understanding chemical recycling of waste polymers, various kinds of zeolites were used as catalysts in the pyrolysis of polypropylene (PP). The effects of zeolites on the degradation temperature and pyrolyzed products of PP were studied. It was found that the degradation temperature of PP strongly depended on the type of zeolite used and the amount added. One type of HY zeolite (320HOA) was shown to be a very effective catalyst. Pyrolysis products, which were identified by using a coupled gas-chromatograph-mass-spectrometer, were also affected by the addition of zeolites. Some zeolites did not change the structure of the products but narrowed the product distribution to a smaller molecule region, while the HY zeolite led to hydrocarbons concentrated at those containing 4-9 carbons. Furthermore, some new compounds with cyclic structures were found in the presence of the HY zeolite. (C) 1996 Elsevier Science Limited

ESCA study of dichlorozirconocene/methylaluminoxane olefin polymerization catalyst system

An investigation has been undertaken by use of ESCA in the characterization of the central metal(Zr) of dichlorozirconocene/methylaluminoxane homogeneous olefin polymerization catalyst. The change of electron density shown by a shift in ESCA signals (181.8 - 182.7eV) indicates that the catalytic species are ''cation-like''. Within the range of detecting sensitivity of ESCA spectrometer, only a part of the new catalytic derivative was formed. The influence of complexion time and Al : Zr ratio on the formation of the catalytic zirconocene cation has also been investigated.

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.

GAS-PHASE SYNTHESIS OF DERIVATIVE OF C-60-C60S+

Gas phase ion-molecular reactions of C-60 with the ion system of CS2 have been studied in the ion source of mass spectrometer. It was found for the first time that the sulfuric derivative of C-60-C60S+ was the main ions in the ion source, they did not react with C-60 to form adduct ions due to their highly saturated structures. According to the dynamic analysis, the product ion came from the reaction of C-60 with the fragment ion S+. The adduct ion may have the structure of epsulfide that is advantageous in energy.

UNIMOLECULAR DISSOCIATION REACTIONS OF DOUBLY-CHARGED IONS [C12H12N2O](2+) AND [C12H12N2S](2+) IN GAS-PHASE

The unimolecular dissociation reactions of doubly charged ions were reported, which resulted from a tandem mass spectrometer and a reversed geometry double focusing mass spectrometer by electron impact, Mass analyzed ion kinetic energy spectrometry (MIKES) was used to obtain the kinetic energy releases in charge separation reactions of doubly charged ions, The intercharge distances between the two charges at transition states can be calculated from the kinetic energy releases, Transition structures of unimolecular dissociation reactions were infered from MIKES and MS/MS.

Gas-phase Ion-molecular Reactions of C-60 and C-70 with Acetone and Quantum Chemistry Study

Gas-phase ion-molecular reactions of C-60 and C-70 with the ion system of acetone have been studied in this paper. The ions of protoned and acetylized C-60 and C-70 were formed by the reactions of C-60 and C-70 with some ions which existed in the ion system when mass spectrometer worked on chemical ionization conditions. The reactivity of C-70 is greater than that of C-60. Results of quantum chemical calculation for the adduct ions showed a sigma bond between the acyl carbon atom and C-60 may be Formed. These results will provide some valuable informations on the condense-phase acetylization of C-60.

APPLICATIONS OF RAPID SCAN SPECTROELECTROCHEMISTRY - DETERMINATION OF HETEROGENEOUS ELECTRON-TRANSFER RATE-CONSTANT OF BILIVERDIN OXIDATION

The rapid scan spectrometer was used to determine the heterogeneous electron transfer rate parameters for the oxidation of Biliverdin in DMF by single potential step thin layer spectroelectrochemical techniques and yielded an average formal heterogeneous electron transfer rate constant K(s, h)0' = 2.45 (+/-0.12) x 10(-4) cm s-1, electrochemical transfer coefficient alpha = 0.694+/-0.008. The oxidation process of Biliverdin was also studied and the formal potential E0 = 0.637 V (vs. Ag/AgCl) was obtained.

KALMAN FILTERING FOR RESOLUTION OF OVERLAPPING LINES IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

A Kalman filter was developed for resolving overlapping lines in inductively coupled plasma atomic emission spectrometry (ICP-AES) and evaluated experimentally with the determination of La in the presence of Ho, and Cu in the presence of Pr. The whiteness of the innovation sequence for an optimal filter was explored to be the criterion for the correction of the wavelength positioning errors which may occur in spectral scans. Under the conditions of the medium-resolution spectrometer and 1.5 pm step size in scans, the filter effectively resolved the Cu/Pr line pair having a small peak separation of 4.8 pm. For the La/Ho line pair with a peak distance of 9.8 pm, an unbiased estimate for La concentration was still obtained even when the signal-to-background ratio was down to 0.048. Favourable detection limits for real samples were achieved. Unstructured backgrounds were modeled theoretically and all spectral scans therefore did not require the correction for solvent.

Geochemistry of rare earth elements in cobalt-rich crusts from the Mid-Pacific M seamount

Rare earth elements (RFEs) and major elements of 25 cobalt-rich crusts obtained from different depths of Mid-Pacific M seamount were analyzed using inductively coupled plasma-atomic emission spectrometer and gravimetric method. The results showed that they were hydrogenous crusts with average Sigma REE content of 2084.69 mu g/g and the light REE (LREE)/heavy REE (HREE) ratio of 4.84. The shale-normalized PEE patterns showed positive Ce anomalies. The total content of strictly trivalent REEs increased with water depth. The Ce content and LREE/HREE ratios in Fe-Mn crusts above 2000 in were lower than those below 2000 m. The change in RE E with water depth could be explained by two processes: adsorptive scavenging by setting matters and behaviors of REE in seawater. However, the Ce abundance took no obvious correlation with water depth reflects the constant Ce flux. The Cc in crusts existed mainly as Ce(IV), implying that the oxidative-enriching process was controlled by kinetic factors.

Enrichment of lanthanides in aragonite

Using the constant addition technique, the coprecipitation of lanthanum, gadolinium, and lutetium with aragonite in seawater was experimentally investigated at 25 degrees C. Their concentrations in aragonite overgrowths were determined by inductive coupled plasma mass spectrometer. All these lanthanides were strongly enriched in aragonite overgrowths. The amount of lanthanum, gadolinium, and lutetium incorporated into aragonite accounted for 57%-99%, 50%-89%, and 40%-91% of their initial total amount, respectively. With the increase of aragonite precipitation rate, more lanthanides were incorporated into aragonite while their relative fraction in aragonite overgrowths decreased consistently. It indicated that the coprecipitation of lanthanides with aragonite was controlled by the kinetics of aragonite precipitation.

The sedimentation rates in the Okinawa trough during the Late Quaternary

On the basis of accelerator mass spectrometer radiocarbon (AMS C-14) dating, sedimentation rates of 11 cores collected from the northern to southern Okinawa Trough are discussed. The sedimentation rates in the Okinawa Trough roughly range from 11 to 39 cm/ka, and the average is 23.0 cm/ka. China's continental matter is the main sediment source of the middle Okinawa Trough and has important contribution to the northern and southern Okinawa Trough. The sedimentation rates during the marine oxygen isotope (MI5) 2 are uniformly higher than those during MIS 1 in the northern and middle Okinawa Trough while they are on the contrary in the southern Okinawa Trough. Sedimentation rates in the Okinawa Trough can be one of the proxies of sediment source and an indicator of cooling events.