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61.
Hoteling AJ Kawaoka K Goodberlet MC Yu WM Owens KG 《Rapid communications in mass spectrometry : RCM》2003,17(14):1671-1676
Details of the optimization of the collision-induced dissociation (CID) process, using a collision cell on a matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometer, are described using poly(ethylene glycol) 1000 (PEG 1000) as a model analyte. The effects of collision gas identity (helium, air, and argon), as well as collision gas pressure, on the resulting MS/MS data were investigated. With PEG 1000, helium was found to give the best results with respect to signal-to-noise (S/N) ratio. The optimum pressure for each gas was found to be in the range where the precursor ion signal was attenuated to approximately 30-50% for helium and 40-60% for argon. The effect of cation choice (Li, Na, and K) on the CID of PEG was also studied. CID spectra were produced for each, but PEG cationized with lithium was found to produce the spectra with the highest S/N ratio. The MALDI-TOF CID spectra that were generated for PEG were compared with the high-energy and low-energy MS/MS spectra obtained from a sector mass spectrometer and from a triple quadrupole mass spectrometer, respectively. The results observed for PEG confirm that CID on a MALDI-TOF mass spectrometer is a high-energy MS/MS technique. 相似文献
62.
Franklin Kevin R. Lowe Barrie M. 《Journal of inclusion phenomena and macrocyclic chemistry》1988,6(6):605-611
The sorption of tetraethyleneglycol by silicalite-1 and triethyleneglycol by silicalite-1 and a silicalite-1/silicalite-2 intergrowth has been studied at 25°C and at fixed water activities in the range 0.111<a
w<0.902 by an isopiestic method. All of the glycol uptakes are between 0.95 and 1.2 molecules per unit cell and in all cases they are essentially independent of water activity. The water content of the silicalite-1 was more sensitive to water activity and glycol content than was that of the silicalite-1/2 intergrowth. 相似文献
63.
The first intermolecular Friedel-Crafts acylation of a variety of aromatic substrates with azetidinones is described. The Friedel-Crafts acylations are performed under very mild conditions, using trifluoromethanesulfonic acid to produce beta-amino aromatic ketones in excellent yields. 相似文献
64.
The reactions of various fluoroaromatics, C6F6?xHx, and C6F5X (X = C6F6, Cl, Me, NO2, CF3, COCl, CH2Br, OMe, and NH2) with lead(II) benzenethiolate in DMF have been examined. Lead thiolate acted as an excellent source of benzenethiolate anions and displacement of fluorine, chlorine or the nitro group was observed. The new products have been characterized by elemental analysis, and NMR (H?1 and F?19), infrared and mass spectroscopy. 相似文献
65.
Janak KE Tanski JM Churchill DG Parkin G 《Journal of the American Chemical Society》2002,124(16):4182-4183
Mo(PMe3)6 reacts with thiophene to give the eta5-thiophene complex (eta5-C4H4S)Mo(PMe3)3 and the eta5-butadiene-thiolate complex (eta5-C4H5S)Mo(PMe3)2(eta2-CH2PMe2), which are the first examples of (i) eta5-thiophene coordination and (ii) C-S cleavage and hydrogenation by a molybdenum compound. Deuterium labeling studies suggest that the hydrogenation of thiophene may involve an alkylidene intermediate, an observation that has ramifications for the mechanisms of hydrodesulfurization. 相似文献
66.
Plieger PG Ehler DS Duran BL Taylor TP John KD Keizer TS McCleskey TM Burrell AK Kampf JW Haase T Rasmussen PG Karr J 《Inorganic chemistry》2005,44(16):5761-5769
The ligand 4,5-dicarboxyimidazole (H(2)DCI) and its methyl derivative 1-methyl-4,5-dicarboxyimidazole (H(2)MDCI) have been shown to bind to Be(II) forming a zwitterionic species that has been structurally characterized. A new dicarboxyimidazole-based polymer has been prepared and its Be-binding properties have been studied using NMR ((1)H and (9)Be) and fluorescence spectroscopy; it represents a rare example of beryllium binding to a polymer. Models of the mononuclear and polymeric Be(II)-binding sites have been studied using density functional theory (DFT), and the (9)Be NMR chemical shifts of these model materials have been calculated for the purpose of direct comparison to experimentally observed values. Differences in the binding modes of the mononuclear and polymeric species are discussed. 相似文献
67.
Simulation of the Adhesion of Particles to Surfaces 总被引:1,自引:0,他引:1
The removal of micrometer and submicrometer particles from dielectric and metal films represents a challenge in postchemical mechanical polishing cleaning. Proper modeling of the adhesive force between contaminant particles and these films is needed to develop optimal solutions to postchemical mechanical polishing cleaning. We have previously developed and experimentally validated a model to describe the adhesion between spherical particles and thin films. This simulation expands previous models to characterize the adhesive interaction between asymmetrical particles, characteristic of a polishing slurry, and various films. Our simulation accounts for the contact area between particles and substrates, as well as the morphology of the surfaces. Previous models fail to accurately describe the contact of asymmetrical particles interacting with surfaces. By properly accounting for nonideal and geometry and morphology, the simulation predicts a more accurate adhesive force than predictions based upon an ideal van der Waals model. The simulation is compared to experimental data taken for both semi-ideal particle-substrate systems (polystyrene latex spheres in contact with silicon films) and asymmetrical systems (alumina particles in contact with various films). Copyright 2001 Academic Press. 相似文献
68.
A MALDI TOF-TOF instrument was optimized and evaluated for intact protein analysis by tandem mass spectrometry. Ion source voltages and delay times were adjusted to affect an up to a 10-fold improvement in fragment ion yield compared to data obtained using default settings employed in peptide analysis. For large peptides (3-4.5 kDa), up to 90% of all possible b- and y-fragment ions were observed, which provides sufficient information for de novo sequencing and unambiguous protein identification. Product ion signals associated with preferential cleavages C-terminal to aspartic acid and glutamic acid residues and N-terminal to proline residues became dominant with increased protein molecular weight. Matrix effects were also evaluated and, among the eight matrices examined, alpha-cyano-4-hydroxycinnamic acid (CHCA) was found to produce the best intact protein tandem mass spectra for proteins up to 12 kDa. Optimized performance yielded detection limits of 50-125 fmol for proteins of 4 and 12 kDa, respectively. This improved performance has yielded an instrument with potential to be a useful tool in proteomic investigations via analysis of intact proteins. 相似文献
69.
Klapars A Waldman JH Campos KR Jensen MS McLaughlin M Chung JY Cvetovich RJ Chen CY 《The Journal of organic chemistry》2005,70(24):10186-10189
[reaction: see text] A mild and transition-metal-free method for the alpha-arylation of aliphatic nitriles with activated heteroaryl halides was developed using NaHMDS or KHMDS as base at ambient temperature. The key to the success of this method is generation of the nitrile anion in the presence of the heteroaryl halide. The method is applicable to both primary and secondary carbonitriles and a wide range of heteroaryl halides. Selective monoarylation was observed with primary carbonitriles. The operational simplicity and the mild reaction conditions add to the value of this method as a practical alternative to the preparation of alpha-heteroaryl carbonitriles. 相似文献
70.
Antihydrophobic cosolvent effects for alkylation reactions in water solution, particularly oxygen versus carbon alkylations of phenoxide ions 总被引:1,自引:0,他引:1
Antihydrophobic cosolvents such as ethanol increase the solubility of hydrophobic molecules in water, and they also affect the rates of reactions involving hydrophobic surfaces. In simple reactions of hydrocarbons, such as the Diels-Alder dimerization of 1,3-cyclopentadiene, the rate and solubility data directly reflect the geometry of the transition state, in which some hydrophobic surface becomes hidden. In reactions involving polar groups, such as alkylations of phenoxide ions or S(N)1 ionizations of alkyl halides, cosolvents in water can have other effects as well. However, solvation of hydrophobic surfaces is still important. By the use of structure-reactivity relationships, and comparing the effects of ethanol and DMSO as solvents, it has been possible to sort out these effects. The conclusions are reinforced by an ab initio computer model for hydrophobic solvation. The result is a sensible transition state for phenoxide ion as a nucleophile, using its oxygen n electrons to avoid loss of conjugation. The geometry of alkylation of aniline is very different, involving packing (stacking) of the aniline ring onto the phenyl ring of a benzyl group in the benzylation reaction. The alkylation of phenoxide ions by benzylic chlorides can occur both at the phenoxide oxygen and on ortho and para positions of the ring. Carbon alkylation occurs in water, but not in nonpolar organic solvents, and it is observed only when the phenoxide has at least one methyl substituent ortho, meta, or para. The effects of phenol substituents and of antihydrophobic cosolvents on the rates of the competing alkylation processes indicate that in water the carbon alkylation involves a transition state with hydrophobic packing of the benzyl group onto the phenol ring. The results also support our conclusion that oxygen alkylation uses the n electrons of the phenoxide oxygen as the nucleophile and does not have hydrophobic overlap in the transition state. The mechanisms and explanations for competing oxygen and carbon alkylations differ from previous proposals by others. 相似文献