共查询到20条相似文献,搜索用时 31 毫秒
1.
Fragmentations induced by collision-activated dissociation of α-O- and α-N-substituted oxazolidines are demonstrated under ammonia chemical ionization (CI) and electron impact (El) conditions. Discrimination of these regioisomers is achieved using either conventional EI mass spectra or daughter ion mass spectra of the protonated molecules under ammonia CI conditions. 相似文献
2.
The mass spectra of 15 azines and 5 phosphazines are investigated by deuterium labelling and high resolution mass measurements. Azines of aldehydes undergo a skeletal rearrangement in which HCN and (HCN + H) are eliminated from the molecular ion. Azines of ketones first eliminate an aryl or alkyl radical and then rearrange with the expulsion of CN. or (CN. + H). Analogies to the photolytic or thermal elimination of nitrogen in azines could not be detected. o,o′-Dinitrobenzaldazin undergoes a double oxygen rearrangement in which carbon dioxide is eliminated. Phosphazines show a similar behaviour under electron-impact as under pyrolytic conditions. 相似文献
3.
Identifying Diffusion Limiting Current to Unravel the Intrinsic Kinetics of Electrode Reactions Affected by Mass Transfer at Rotating Disk Electrode
下载免费PDF全文
![点击此处可从《化学物理学报(中文版)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Rotating disk electrode systems are widely used to study the kinetics of electrocatalytic reactions that may suffer from insufficient mass transfer of the reactants. Kinetic current density at certain overpotential calculated by the Koutecky-Levich equation is commonly used as the metrics to evaluate the activity of electrocatalysts. However, it is frequently found that the diffusion limiting current density is not correctly identified in the literatures. Instead of kinetic current density, the measured current density normalized by diffusion limiting current density (j/jL) has also been frequently under circumstance where its validity is not justified. By taking oxygen reduction reaction/hydrogen oxidation reaction/hydrogen evolution reaction as examples, we demonstrate that identifying the actual diffusion limiting current density for the same reaction under otherwise identical conditions from the experimental data is essential to accurately deduce kinetic current density. Our analysis reveals that j/jL is a rough activity metric which can only be used to qualitatively compare the activity trend under conditions that the mass transfer conditions and the roughness factor of the electrode are exactly the same. In addition, if one wants to use j/jL to compare the intrinsic activity, the concentration overpotential should be eliminated. 相似文献
4.
P. Goldberg J. A. Hopkinson A. Mathias A. E. Williams 《Journal of mass spectrometry : JMS》1970,3(8):1009-1021
The n-alkanes, propane to heptane, have been studied in a modified MS-9 mass spectrometer under conditions that enabled the daughter ions, resulting from metastable fragmentation processes occurring in the first field free region, to be observed with high sensitivity. The precursor ions in these fragmentations have been identified unambiguously and a general fragmentation scheme for the n-alkanes is proposed. The mass spectrometer incorporated a variable width monitor slit and narrow settings of this slit improved the energy resolution so that fine structure could be observed in some of the ‘metastable peaks’. The implications of this fine structure are discussed. 相似文献
5.
The branching ratios for the reaction pathways of 39 polychlorinate dibenzo-p-dioxins (PCDDs) under oxygen negative chemical ionization/atmospheric pressure ionization mass spectrometric conditions were measured. These results demonstrated that the PCDDs could be separated into 14 groups by this technique. These results were compared with those reported previously for 14 PCDDs using oxygen negative chemical ionization mass spectrometry. 相似文献
6.
Guido Audisio Maria Grassi Sergio Daolio Pietro Traldi 《Journal of mass spectrometry : JMS》1984,19(5):221-226
Not only strong differences in relative abundances of product ions, but also different fragmentation pathways are observed in the electron impact mass spectrosopy of six stereoisomeric cyclohexanehexacarboxylic methyl esters. This unusual behaviour has been studied in detail with the aid of different ionization methyods, B/E and B2/E linked scans, exact mass measurements, deuterium labelling experiments and collisionally activated decomposition spectrometry. A close analogy between the isomerization observed under acidic conditions in condensed phase and that observed under chemical ionization (CH4) conditions is underlined. 相似文献
7.
S. A. Pergantis C. A. Emond L. L. Madilao G. K. Eigendorf 《Journal of mass spectrometry : JMS》1994,29(8):439-444
Desorption chemical ionization mass spectrometry employing ammonia as the reagent gas has been extensively used to obtain molecular mass and structural information on a wide variety of compounds. Mass-deficient reference standards normally used for calibration purposes in mass spectrometry do not provide adequate mass spectra under ammonia chemical ionization conditions. In order to overcome this problem a mixture of ammonia and methane as reagent gases was employed. In high-resolution accurate mass measurement experiments, this gas mixture allows the simultaneous detection of mass spectra of perfluorokerosene adequate for calibration purposes and spectra containing molecular mass information of the analyte. A needle valve system was used to control the composition of the gas mixture introduced into the ion source. For positive-ion accurate mass measurements of higher masses (up to m/z = 2300), Fomblin 18/8 oil was successfully used as a reference standard under ammonia, methane and isobutane desorption chemical ionization conditions. 相似文献
8.
K. P. Madhusudanan Shubhra Mittal S. Durani R. S. Kapil 《Journal of mass spectrometry : JMS》1985,20(3):215-222
The electron impact (EI) and chemical ionization (CI) mass spectra of certain 1,2,3-triaryl-2-propen-1-ones (TAPs) have been studied in detail with the help of exact mass measurements, deuterium labelling and metastable data. The E- and Z-isomeric pairs do not show any difference in their behaviour under EI or CH4 CI conditions. EI-induced rearangement reactions in the TAPs include aryl migration to carbonium ion centres. A study of the metastable transitions reveals aryl group interchange in the molecular ions prior to fragmentation. Under EI conditions loss of arene involves either C(2) or C(3) aryl groups while under CI conditions the C(1) aryl is lost as a neutral arene molecule. Mechanisms for the different fragmentation modes are given. 相似文献
9.
Batch suspension cultures ofCatharanthus roseus G. Don were grown in a 5 L LKB Ultraferm fermenter, converted to operate as an airlift bioreactor, to test the suitability of such
a system for the mass culture of plant cells. Results show that the airlift system has considerable merits as a culture vessel
for such a purpose, including: conversion rates of carbohydrate substrate to cell mass equivalent to > 50% under optimum conditions.
(Operating under these conditions, growth rates of approximately 0.4 d-1 are typical). In the absence of the mechanical shear normally associated with mechanically driven bioreactors, the gently
agitated environment of the airlift vessel proves to be an ideal system for the growth of fragile plant cells. Use of a nozzle
sparger reduces the possibility of a high mass transfer coefficient, except at very high gassing rates, thereby eliminating
any interference with the growth rate caused by high rates of gaseous exchange. 相似文献
10.
Vijaya Madhyanapu Golla Mallika Kalyan Upasana Gholap Hara Prasad Padhy Roshitha K. Ramachandran Gananadhamu Samanthula 《Journal of mass spectrometry : JMS》2024,59(3):e5007
The present study aimed to separate, identify, and characterise the degradation products formed when mavacamten is exposed to stress degradation as well as the stability of the drug in various environments and also to understand its degradation chemistry. Prediction of in silico toxicity and mutagenicity was aimed at the observed degradation products. Stress degradation along with stability studies and degradation kinetics were performed on mavacamten, and separation of degradation products was carried out by high-performance liquid chromatography. Tandem mass spectrometry studies were executed to characterise the structures of degradation products using product ion fragments. Orthogonally, nuclear magnetic resonance experiments were conducted to elucidate the structures having ambiguity in characterising them. Deductive Estimation of Risk from Existing Knowledge and Structure Activity Relationship Analysis using Hypotheses software were used to establish in silico toxicity and mutagenic profiles of mavacamten and its degradation products. Two degradation products of mavacamten found in acidic hydrolytic stress conditions were separated, identified, characterised, and proposed as 1-isopropylpyrimidine-2,4,6(1H,3H,5H)-trione and 1-phenylethanamine. Mavacamten was found to be stable under different pH and gastrointestinal conditions. The degradation kinetics of mavacamten under 1 N acidic condition followed zero-order kinetics, and it was degraded completely within 6 h. In silico toxicity and mutagenicity studies revealed that 1-phenylethanamine can be a skin sensitiser. A high-performance liquid chromatography method was developed for the separation of degradation products of mavacamten and characterised by liquid chromatography–tandem mass spectrometry and nuclear magnetic resonance. During the manufacturing and storage of drug product, precautions need to be taken when dealing with acidic solutions as the drug is prone to hydrolysis in acidic conditions. The formation of 1-phenylethanamine under these conditions is to be monitored as it is a skin sensitiser. 相似文献
11.
Alfred J. Vella 《Journal of mass spectrometry : JMS》1992,27(2):145-150
An investigation of the quality of mass spectra obtainable by the Finnigan ion-trap detector (ITD) and on how this quality may depend on sample size is described. For compounds which are not very thermolabile or too prone to fragmentation, near-normal spectra can be expected if the sample sizes do not exceed amounts of the order of 100 ng. Analyte loads which generate acceptable total ion current chromatograms with narrow-bore capillary columns (about 500 ng) could still produce ITD mass spectra having enhanced quasi-molecular ions, [M + 1]+, abnormal distributions of peak intensities and unusual fragments. Even under optimum conditions, certain analytes, e.g. acyclic alkanes, n-alkanols and pyridines, will manifest spectral characteristics which are strictly typical of the ITD. In favourable cases, the formation of quasi-molecular ions can be exploited for relative molecular mass determination. Even under conditions of self-chemical ionization, the ITD spectra of most analytes generally retain enough electron impact mass spectral character to be readily recognizable by inspection or by library algorithms. 相似文献
12.
Ricky Lam Michael A. Rogers Alejandro G. Marangoni 《Journal of Thermal Analysis and Calorimetry》2009,98(1):7-12
The physical properties of a fat are determined by its thermal history, processing conditions, chemical composition, polymorphism
and spatial distribution of mass. The mass fractal dimension of a fat crystal network can be determined from the slope of
the log–log plot of the storage modulus (G′) versus the solid fat content (SFC). Different SFCs were obtained by melting the fat, diluting it to different extents in
liquid oil, and crystallizing the blends under specific conditions. One of the major drawbacks of this method is the inability
of characterizing the native structure of an already crystallized fat. In the thermo-mechanical method developed in this study,
SFC is changed via temperature variations instead. At each temperature, the G′ and SFC were measured and the fractal dimension calculated as described above. The thermomechanical method proved to be
a simpler and more reliable estimator of the fractal dimension of a fat crystal network than the dilution method. 相似文献
13.
Walter A. Korfmacher Claude L. Holder James P. Freeman Ronald K. Mitchum Aubrey B. Gosnell 《Journal of mass spectrometry : JMS》1985,20(7):435-439
The chemical ionization mass spectrometric (CIMS) analysis of doxylamine, N,N-dimethyl-2-[1-phenyl-1-(2-pyridinyl)ethoxy]ethanamine, and related compounds, using both ammonia and methane as reagent gases, is discussed. The two reagent gases did not produce the same major fragment ion for doxylamine. Mechanisms for the fragmentation of doxylamine under either ammonia or methane CIMS conditions are proposed. The mechanisms explain the observation of an m/z 182 fragment ion for doxylamine analyzed under methane CIMS conditions and an m/z 184 product ion detected under ammonia CIMS conditions. 相似文献
14.
Ronda D. Davis Timothy D. Nelson Wendel L. Nelson 《Journal of heterocyclic chemistry》1994,31(6):1509-1511
During alkylation of 3-O-benzyl-6α-naltrexol ( 1 ) with large aralkyl halides like 2-bromomethylnaphthalene and 9-chloromethylanthracene under phase transfer catalysis conditions (potassium hydroxide, tetrabutylammonium bromide, methylene chloride), formation of a new 6α,14-epoxide-bridged isomorphinan ( 4 ) was noted. Chemical and spectral evidence, including nmr and mass spectral data, are presented to prove its structure. Its formation results from 6α-oxygen displacement of a 14-O-aralkyl ether intermediate under the phase transfer catalysis alkylation conditions. 相似文献
15.
The kinetics of the esterification of lauric acid with geraniol catalyzed by a commercially immobilized lipase preparation
fromMucor miehei, Lipozyme, was studied in well-stirred flasks under conditions of no external mass transfer limitations. It was shown that
the reaction is inhibited by lauric acid and the reaction mechanism can be described as a Ping-Pong Bi-Bi with Dead-End inhibition
caused by lauric acid. 相似文献
16.
In this research paper, an eco-friendly extraction process of dyes from Vicia faba L. membranes was developed. In this regard, the influence of independent process factors like the weight of material, the extraction time, the temperature and the sodium hydroxide concentration on the natural dye extraction from Vicia faba membranes was investigated. The optimisation of the extraction conditions and the effect evaluation of the different operating parameters were carried out using a Box–Behnken design under response surface methodology. The optimum conditions were found to be 66 °C, 90 min, 5 g and 0.1628 mol·L?1 for extraction temperature, time, mass of the material and sodium hydroxide concentration, respectively. The efficiency of this extraction process under these optimum conditions was evaluated by measuring the total phenolic content (TPC), the total flavonoid content and the relative colour yield (K/S). In these operating conditions, good fastness ratios were observed for the dyed fabrics. 相似文献
17.
The mass spectra of organogermanium compounds of the type PhnGeCl4-n (where n = 1–4) were investigated. Positive and negative ion spectra of these compounds were recorded using conventional electron impact (EI) conditions. In common with the analogous tetra-alkyltin compound, Ph4Ge produced no negative ion spectra under these conditions. Tandem mass spectrometry (MS–MS) was used to deduce fragmetation reaction pathways for these compounds. In the case of PhGeCl3, collision-induced dissociation studies were extended to examine the ion–molecule reactions under relatively high reactant pressures of methanol and/or water vapour in the collision cell of the MS–MS instrument. 相似文献
18.
The charge-reversal (CR) mass spectra of the enolate ions of heptanal and ten isomeric heptanones, of cyclohexanone, of cycloheptanone, of isomeric methylcyclohexanones, of isomeric ethylcyclohexanones and of the iso meric monoterpene ketones camphor, fenchone, pulegone and thujone were obtained by deprotonation using OH? under chemical ionization conditions followed by collision of the [M ? H] ? ions with helium in the second field-free region of a VG ZAB 2F mass spectrometer. The CR mass spectra were evaluated by similarity index (SI) values. Characteristic of the CR mass spectra of the open-chain enolates are fragment ions formed by α-cleavage. However, the CR mass spectra are dominated by peaks of small hydrocarbon ions, particularly in the case of cyclic and bicyclic enolates. The CR mass spectra of enolates of linear heptanones differing in the position of the carbonyl group can be easily correlated with the structure of the parent ketone. The CR mass spectra of enolates of isomeric heptan-2-ones differing only in the degree of branching of the alkyl group are similar, but can be distinguished by the SI values. The CR mass spectra of the enolates of the isomeric cyclic and bicyclic ketones studied are more or less identical and cannot be used for structural assignment. 相似文献
19.
Alexander A. Aksenov James T. Kapron 《Rapid communications in mass spectrometry : RCM》2010,24(10):1392-1396
High‐field asymmetric waveform ion mobility spectrometry (FAIMS) is an ion‐filtering technique recently adapted for use with liquid chromatography/mass spectrometry (LC/MS) to remove interferences during analysis of complex matrices. This is the first systematic study of a series of singly charged tetraalkylammonium ions by FAIMS‐MS. The compensation voltage (CV) is the DC offset of the waveform which permits the ion to emerge from FAIMS and it was determined for each member of the series under various conditions. The electrospray ionization conditions explored included spray voltage, vaporizer temperature, and sheath and auxiliary gas pressure. The FAIMS conditions explored included carrier gas flow rate, electrode temperature and composition of the carrier gas. Optimum desolvation was achieved using sufficient carrier gas (flow rate ≥2 L/min) to ensure stable response. Low‐mass ions (m/z 100–200) are more susceptible to changes in electrode temperature and gas composition than high mass ions (m/z 200–700). As a result of this study, ions are reliably analyzed using standard FAIMS conditions (dispersion voltage ?5000 V, carrier gas flow rate 3 L/min, 50% helium/50%nitrogen, inner electrode temperature 70°C and outer electrode temperature 90°C). Variation of FAIMS conditions may be of great use for the separation of very low mass tetraalkylammonium (TAA) ions from other TAA ions. The FAIMS conditions do not appear to have a major effect on higher mass ions. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
20.
Roger J. Greathead Rod S. Mason Keith R. Jennings Janet A. Page Robert J. Pryce 《Journal of mass spectrometry : JMS》1985,20(2):110-114
The behaviour of gibberellic acid (GA3) under electron impact and chemical ionization conditions has been examined. The tendency of GA3 to undergo pyrolysis by the loss of the elements of water and carbon dioxide has been identified. Two methods of sample introduction can be used to minimize the occurrence of this pyrolysis. Accurate mass measurement allows the composition of the pyrolysis product to be determined and metastable techniques confirm the structure of this product to be epi-allogibberic acid rather than its isomer allogibberic acid. This result corrects a misconception in the literature and illustrates the advantage of metastable methods compared with accurate mass measurements, for the determination of small structural differences within a molecule. 相似文献