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991.
Bristow AW Nichols WF Webb KS Conway B 《Rapid communications in mass spectrometry : RCM》2002,16(24):2374-2386
Mass spectral libraries provide a tool for identifying unknown compounds using both molecular weight and fragmentation information. Mass spectrometers with electrospray ionisation (ESI) and atmospheric chemical ionisation (ApCI) sources have the capability to produce data of this type using in-source collisionally induced dissociation (CID), and in-source CID libraries can be created. Due to the variation in electrospray source design from different instrument manufacturers, the production of reproducible in-source CID spectra that can be used in libraries for all instrument types is not a trivial task. To date, the evaluation of the production of in-source CID libraries has tended to focus on similar instruments from one manufacturer. The studies have also tended to focus on specific compound classes, with a limited molecular weight range.This report describes the findings from the investigation of protocols for the creation of mass spectral libraries using ESI in-source CID on six instruments from four different manufacturers. The overall goal was to create a spectral library for the identification of unknowns. The library could then be applied across all manufacturers' electrospray instruments.Two different experimental protocols were attempted. The first used a tuning compound to establish standard ESI source conditions, with fixed fragmentation potentials. The second involved the attenuation of the [M + H](+) ion to a known degree. A diverse range of compounds (pharmaceutical, photographic, pesticides) was tested to establish the reproducibility of the spectra on the six instruments. Both protocols produced spectra on the various instruments that in many cases were very similar. In other examples, the spectra differed not only in their relative ion abundances, but also in terms of the spectral content. Important observations regarding the effect of ion source design are also reported.The degree of spectral reproducibility was calculated off-line by comparing the five most abundant ions (20% for each ion that matches) from each spectrum on each instrument. This approach was adopted, as we do not possess a software package that met our requirements for spectral comparison. Match factors (% fit) were calculated by comparing each spectrum against the spectra recorded for the same compound and then for all other compounds, on each instrument. The % fit values derived by the off-line approach gave a clear view of the spectral reproducibility from instrument to instrument and also discriminated the spectra of the various compounds from each other. The applicability of this approach was tested using a blind trial in which several compounds were presented as unknowns, their in-source CID spectra recorded and the five-ion approach used for identification. 相似文献
992.
In spite of great commercial importance of the Phillips CrOx/SiO2 catalyst and long term research efforts, the precise physicochemical nature of active sites and polymerization mechanisms
still remains unclear. The difficulties in a clear mechanistic understanding of this catalyst mainly come from the complexity
of the surface chemistry of the amorphous silica gel support. In this work, novel silsesquioxane-supported Phillips Cr catalysts
are utilized as realistic models of the industrial catalyst for theoretical investigation using the density functional theory
(DFT) method in order to elucidate the effects of surface chemistry of silica gel in terms of supporting of chromium compounds
and fluorination of the silica surface on the catalytic properties of the Phillips catalyst. Both qualitative and quantitative
aspects with respect to various electronic properties and thermodynamic characteristics of the model catalysts were achieved.
The future prospects of a state-of-the-art catalyst design and mechanistic approaches for the heterogeneous SiO2-supported Phillips catalyst has been demonstrated.
The text was submitted by the authors in English. 相似文献
993.
(all-Z)-(9,10,12,13,15,16-2H6)Octadeca-9,12,15-trienoic acid ( = α-linolenic acid; D6- 4 ) was synthesized to investigate the biochemical formation of linolenic-acid-derived aroma compounds in cultures of the yeast Sporobolomyces odorus, using an established gas chromatographic/mass spectrometric (GC/MS) method. Three compounds were identified as labeled: (Z)-dec-7-eno-5-lactone (δ-jasmin lactone), (Z,Z)-dodeca-6,9-dieno-4-lactone, and (2E,4Z)-hepta-2,4-dienoic acid. Both lactones were biosynthesized mostly under conservation of the initial configuration from their corresponding oxygenated linolenic-acid intermediates. The application of (13S,9Z,11E,15Z)-13-hydroxy(9,10,12,13,15, 16-2H6)octadeca-9,11,15-trienoic acid (D6- 7 ) as a OH-functionalized precursor of δ-jasmin lactone allowed to gain insight into the stereochemical course of the biosynthesis to both enantiomers of this lactone. In this experiment, 88.3% of the metabolized labeled precursor was transformed under retention of the original configuration of the (R)-enantiomer. This investigation is also a contribution to a better understanding of the C?C bond isomerization steps which took place during the β-oxidative degradation of the substrate. 相似文献
994.
James V. Beitz C.W. Williams K.-S. Hong G.K. Liu 《Journal of solid state chemistry》2005,178(2):511-520
We have assessed the feasibility of carrying out time- and wavelength-resolved laser-induced fluorescence measurements of radiation damage in glassy silica. The consequences of alpha decay of Es-253 in LaPO4 nanophases embedded in silica were probed based on excitation of 5f states of Cm3+, Bk3+, and Es3+ ions. The recorded emission spectra and luminescence decays showed that alpha decay of Es-253 ejected Bk-249 decay daughter ions into the surrounding silica and created radiation damage within the LaPO4 nanophases. This conclusion is consistent with predictions of an ion transport code commonly used to model ion implantation. Luminescence from the 6D7/2 state of Cm3+was used as an internal standard. Ion-ion energy transfer dominated the dynamics of the observed emitting 5f states and strongly influenced the intensity of observed spectra. In appropriate sample materials, laser-induced fluorescence provides a powerful method for fundamental investigation of alpha-induced radiation damage in silica. 相似文献
995.
Characterization of nanostructured hollow polymer spheres with small-angle neutron scattering (SANS)
Hollow polymer spheres synthesized from a vesicle-directed polymerization can be dried and redispersed in water using a variety of nonionic ethoxylated alcohol surfactants as stabilizers. The final dispersions consist of both polymer shells and surfactant micelles, which remain together in colloidal suspension for at least several months. Small-angle neutron scattering (SANS) is used to measure the polymer shell thickness (63 A) and core radius (560 A) of the surfactant-stabilized hollow polymer spheres in the presence of surfactant micelles. Characterization by SANS provides information about the surfactant bilayer and polymer shell thicknesses which were previously unattainable. 相似文献
996.
1. | From MNDO quantum chemical calculations, opening of the episulfonium ion ring by neutral nucleophiles X (X=NH3 and HCN) and related SN2 reactions of protonated methylthiol (PMT) with X proceed through formation of pre-reaction complexes in which X is coordinated either at the reacting C atom or (only in opening of episulfonium ion rings) at the center of the C-C bond. |
2. | In their electronic structure, the transition states for the reactions are reminiscent of a carbocation simultaneously reacting with the attacking and the leaving nucleophilic fragments (X S). |
3. | Opening of episulfonium ion rings proceeds slightly more easily (Ea 10–12 kcal/mole) than substitution in PMT (Ea 22–25 kcal/mole). The ease of ring opening for episulfonium ions is due to the large exothermicity of the reaction and the lower internal activation barrier compared with SN2 reactions in PMT. |
997.
Experimental details describing the addition of CF3OF to hexa-
-accetyl-
-lactal (I) are presented. Four fluorinated disaccharides: trifluoromethyl 3,6-di-
-acetyl-2-fluoro-4-
-(2′,3′,4′,6′-tetra-
-acetyl-β-D-galactopyranosyl)-β-
-mannopyrinoside (V), trifluoromethyl 3,6-di-
-acetyl-2-deoxy-2-fluoro-4-
-(2′,3′,4′,6′-tetra-
-acetyl-β-D-galactopyranosyl)-α-
-glucopyranoside (VI), 3,6-di-
-acetyl-2-deoxy-2-fluoro-4-
-(2′,3′,4′,6′-tetra-
-acetyl-β-
-galactopyranosyl)-β-
-mannopyranosyl fluoride (VII), and 3,6-di-
-acetyl-2-deoxy-2-fluoro-4-
-(2′,3′,4′,6′-tetra-
-acetyl-β-D-galactopyranosyl)-α-
-glucopyranosyl fluoride (VIII) were isolated from the product mixture. The profound changes in both the rate and the major products of the addition, compared to those reported for related monosaccharide glycals, are discussed in relation to the steric influence exerted by the presence of the non-reducing (galactoside-B) ring of the disacchride glycals. The configuration and the confirmation of the fluorinated portion of the adducts were assigned on the basis of 19F.m.r. spectroscopic parameters and the structural 相似文献
998.
Starting from 3-oxo-17β-hydroxy-Δ1-5α-androstene (2b) the preparation of 1-oxo-2-methoxy-4α-methyl-17β-hydroxy-Δ2-5α-androstene (9), a compound with the ring A structure of quassine (1) is described. The key problem of the reaction sequence is shown to be the monomethylation at C(4). 相似文献
999.
Reactions of α,β-epoxy ketones with nucleophilic bases generally take one of two courses: (1) α-displacement followed by β-elimination of water or (2) Favorskii rearrangement via a cyclopropanone or zwitterion intermediate. Among the factors that appear to control these reactions, it is suspected that an α′-substituent effect may operate. Such an effect has been confirmed by observing the conversion of 3,5,5,6 - tetramethyl - 2,3 - epoxycyclohexanone (1) to the ring-contracted γ-lactone 3, together with other Favorskii rearrangement products, on treatment with refluxing methanolic potassium hydroxide. The α′-methyl substituted steroid 2 under similar reaction conditions was transformed into roughly equal amounts of 4, 5 and 4 (all rationalized by a Favorskii-like mechanism). In each case the analogous epoxy ketone lacking an α′-Me substituent failed to give any Favorskii products. 相似文献
1000.
Cholesteryl end-capped thermally responsive amphiphilic polymers with two different hydrophobic/hydrophilic chain-length ratios were synthesized from the hydroxyl-terminated random poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) and cholesteryl chloroformate. The hydroxyl-terminated precursor polymers with narrow molecular weight distributions were synthesized by free-radical polymerization using 2-hydroxyethanethiol as a chain-transfer agent. The aqueous solutions of the cholesteryl end-capped copolymers exhibited reversible phase transitions at temperatures slightly above human body temperature, with the lower critical solution temperature values being 37.7 and 38.2 degrees C, respectively. The critical micelle concentration values of the two cholesteryl end-capped polymers were 9 and 25 mg/L, respectively. Polymeric micellar nanoparticles were prepared from the amphiphilic polymers using a dialysis method as well as a direct dissolution method. Transmission electron microscope studies showed that the micellar nanoparticles existed in different morphologies, including spherical, star-like, and cuboid shapes. Pyrene as a model hydrophobic compound could be readily encapsulated in these polymeric nanoparticles, at loading levels of 1.0 and 0.8 mg/g for the two cholesteryl end-capped polymers, respectively. The temperature sensitivity and unusual morphology of these novel polymeric nanoparticles would make an interesting drug delivery system. 相似文献