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111.
Bogdan Bogdanov Henri E. K. Matimba Steen Ingemann Nico M. M. Nibbering 《Journal of the American Society for Mass Spectrometry》1996,7(7):639-652
The mechanism of propene loss from protonated phenyl n-propyl ether and a series of mono-, di-, and trimethylphenyl n-propyl ethers has been examined by chemical ionization (CI) mass spectrometry in combination with tandem mass spectrometry experiments. The role of initial proton transfer to the oxygen atom and the aromatic ring, respectively, has been probed with the use of deuterated CI reagents, D2O, CD3OD, and CD3CN (given in order of increasing proton affinity), in combination with deuterium labeling of the β position of the n-propyl group or the phenyl ring. The metastable [M + D]+ ions of phenyl n-propyl ether—formed with D2O as the CI reagent—eliminate C3H5D and C3H6 in a ratio of 10:90, which indicates that the added deuteron is incorporated to a minor extent in the expelled neutral species. In the experiments with CD3OD as the CI reagent, the ratio between the losses of C3H5D and C3H6 from the metastable [M + D]+ ions of phenyl n-propyl ether is 18:82, whereas the ratio becomes 27:73 with CD3CN as the reagent. A similar trend in the tendency to expel a propene molecule that contains the added deuteron is observed for the metastable [M + D]+ ions of phenyl n-propyl ether labeled at the β position of the alkyl group. Incorporation of a hydrogen atom that originates from the aromatic ring in the expelled propene molecule is of negligible importance as revealed by the minor loss of C3H5D from the metastable [M + H]+ ions of C6D5OCH2CH2CH3 irrespective of whether H2O, CH3OH, or CH3CN is the CI reagent. The combined results for the [M + D]+ ions of phenyl n-propyl ether and deuterium-labeled analogs are suggested to be in line with a model that assumes that propene loss occurs not only from species formed by deuteron transfer to the oxygen atom, but also from ions generated by deuteron transfer to the ring. This is substantiated by the results for the methyl-substituted ethers, which reveal that the position as well as the number of methyl groups bonded to the ring exert a marked effect on the relative importances of the losses of C3H5D and C3H6 from the metastable [M + D]+ ions of the unlabeled methyl-substituted species. 相似文献
112.
Analysis of the distribution of diffusion coefficients in cat brain at 9.4 T using the inverse Laplace transformation 总被引:2,自引:0,他引:2
In this work, the usefulness of the inverse Laplace transformation (ILT) in the characterization of diffusion processes in the brain has been investigated. The method has been implemented on both phantom and in vivo cat brain data acquired at high resolution at 9.4 T. The results were compared with monoexponential and biexponential analyses of the same data. It is shown that in the case of diffusion restricted by white matter axonal tracts, the resulting diffusograms are in good agreement with the biexponential model. In gray matter, however, the non-monoexponential decay does not lead to a bimodal distribution in the ILT, even though the data can be fitted to a biexponential. This finding suggests the possibility of a distribution of diffusion coefficients rather than a discrete biexponential behavior. It is shown that this distribution is sensitive, for example, to experimental parameters such as the diffusion time. Thus, the ILT offers the possibility of implementing a unique tool for the analysis of heterogeneous diffusion, that is, the analysis of the diffusion coefficient distribution, which has the yet unexplored potential of being a valuable parameter in the characterization of tissue structure. 相似文献
113.
In a preceding study a new technique to non-invasively measure the bladder volume on the basis of non-linear wave propagation was validated. It was shown that the harmonic level generated at the posterior bladder wall increases for larger bladder volumes. A dedicated transducer is needed to further verify and implement this approach. This transducer must be capable of both transmission of high-pressure waves at fundamental frequency and reception of up to the third harmonic. For this purpose, a multi-layer transducer was constructed using a single element PZT transducer for transmission and a PVDF top-layer for reception. To determine feasibility of the multi-layer concept for bladder volume measurements, and to ensure optimal performance, an equivalent mathematical model on the basis of KLM-circuit modeling was generated. This model was obtained in two subsequent steps. Firstly, the PZT transducer was modeled without PVDF-layer attached by means of matching the model with the measured electrical input impedance. It was validated using pulse-echo measurements. Secondly, the model was extended with the PVDF-layer. The total model was validated by considering the PVDF-layer as a hydrophone on the PZT transducer surface and comparing the measured and simulated PVDF responses on a wave transmitted by the PZT transducer. The obtained results indicated that a valid model for the multi-layer transducer was constructed. The model showed feasibility of the multi-layer concept for bladder volume measurements. It also allowed for further optimization with respect to electrical matching and transmit waveform. Additionally, the model demonstrated the effect of mechanical loading of the PVDF-layer on the PZT transducer. 相似文献
114.
Steen RG Hunte M Traipe E Hurh P Wu S Bilaniuk L Haselgrove J 《Magnetic resonance imaging》2004,22(3):299-306
Measurement of tissue spin lattice relaxation time (T(1)) has been used to characterize brain development in healthy children. Here we report the first study of brain T(1) in young children with sickle cell disease (SCD). The T(1) in 10 tissue samples was measured by established techniques; 46 SCD patients under the age of 4 years were compared to 267 controls, including 55 well children under the age of 4 years. A model was developed to predict the relationship between age and brain T(1) in controls, then we compared patient T(1) to healthy normal T(1). Most white matter and gray matter tissues in infant patients (<2 years old), had T(1) values significantly higher than normal. For example, 15.0% of patient caudate T(1) values were above the upper bound of the 95% confidence interval for controls, but only 2.5% of normal values are expected to be this high (p = 0.0003). Among infant patients, brain T(1) was significantly higher than normal in every tissue (p < 0.01) except cortical gray matter. However, patient T(1) values declined rapidly to values lower than normal by about age 4. Our findings imply that patients follow an abnormal developmental trajectory beginning early in infancy. 相似文献
115.
Poehlsgaard J Harpsøe K Jørgensen FS Olsen L 《Journal of chemical information and modeling》2012,52(2):409-419
The binding affinity of a drug-like molecule depends among other things on the availability of the bioactive conformation. If the bioactive conformation has a significantly higher energy than the global minimum energy conformation, then the molecule is unlikely to bind to its target. Determination of the global minimum energy conformation and calculation of conformational penalties of binding is a prerequisite for prediction of reliable binding affinities. Here, we present a simple and computationally efficient procedure to estimate the global energy minimum for a wide variety of structurally diverse molecules, including polar and charged compounds. Identifying global energy minimum conformations of such compounds with force field methods is problematic due to the exaggeration of intramolecular electrostatic interactions. We demonstrate that the global energy minimum conformations of zwitterionic compounds generated by conformational analysis with modified electrostatics are good approximations of the conformational distributions predicted by experimental data and with molecular dynamics performed in explicit solvent. Finally the method is used to calculate conformational penalties for zwitterionic GluA2 agonists and to filter false positives from a docking study. 相似文献
116.
Chernyy S Bousquet A Torbensen K Iruthayaraj J Ceccato M Pedersen SU Daasbjerg K 《Langmuir : the ACS journal of surfaces and colloids》2012,28(25):9573-9582
Redox grafting of aryldiazonium salts containing redox units may be used to form exceptionally thick covalently attached conducting films, even in the micrometers range, in a controlled manner on glassy carbon and gold substrates. With the objective to investigate the mechanism of this process in detail, 1-anthraquinone (AQ) redox units were immobilized on these substrates by electroreduction of 9,10-dioxo-9,10-dihydroanthracene-1-diazonium tetrafluoroborate. Electrochemical quartz crystal microbalance was employed to follow the grafting process during a cyclic voltammetric sweep by recording the frequency change. The redox grafting is shown to have two mass gain regions/phases: an irreversible one due to the addition of AQ units to the substrate/film and a reversible one due to the association of cations from the supporting electrolyte with the AQ radical anions formed during the sweeping process. Scanning electrochemical microscopy was used to study the relationship between the conductivity of the film and the charging level of the AQ redox units in the grafted film. For that purpose, approach curves were recorded at a platinum ultramicroelectrode for AQ-containing films on gold and glassy carbon surfaces using the ferro/ferricyanide redox system as redox probe. It is concluded that the film growth has its origin in electron transfer processes occurring through the layer mediated by the redox moieties embedded in the organic film. 相似文献
117.
Bousquet A Ceccato M Hinge M Pedersen SU Daasbjerg K 《Langmuir : the ACS journal of surfaces and colloids》2012,28(2):1267-1275
Thick conductive layers containing anthraquinone moieties are covalently immobilized on gold using redox grafting of the diazonium salt of anthraquinone (i.e., 9,10-dioxo-9,10-dihydroanthracene-1-diazonium tetrafluoroborate). This grafting procedure is based on using consecutive voltammetric sweeping and through this exploiting fast electron transfer reactions that are mediated by the anthraquinone redox moieties in the film. The fast film growth, which is followed by infrared reflection absorption spectroscopy, atomic force microscopy, X-ray photoelectron spectroscopy, ellipsometry, and coverage calculation, results in a mushroom-like structure. In addition to varying the number of sweeps, layer thickness control can easily be exerted through appropriate choice of the switching potential and sweep rate. It is shown that the grafting of the diazonium salt is essentially a diffusion-controlled process but also that desorption of physisorbed material during the sweeping process is essentially for avoiding blocking of the film due to clogging of the electrolyte channels in the film. In general, sweep rates higher than 0.5 V s(-1) are required if thick, porous, and conducting films should be formed. 相似文献
118.
Jiang H Lykke L Pedersen SU Xiao WJ Jørgensen KA 《Chemical communications (Cambridge, England)》2012,48(57):7203-7205
An efficient electromediated aerobic ipso-hydroxylation reaction of aryl and alkyl boronic acids has been developed. Furthermore, mechanistic insight into the role of superoxide anions in this reaction has also been provided based on electrochemical studies and experimental results. 相似文献
119.
María D. Ramos Payán Henrik Jensen Nickolaj Jacob Petersen Steen Honoré Hansen Stig Pedersen-Bjergaard 《Analytica chimica acta》2012
In this work, a microfluidic-chip based system for liquid-phase microextraction (LPME-chip) was developed. Sample solutions were pumped into the LPME-chip with a micro-syringe pump at a flow rate of 3–4 μL min−1. Inside the LPME chip, the sample was in direct contact with a supported liquid membrane (SLM) composed of 0.2 μL dodecyl acetate immobilized in the pores of a flat membrane of polypropylene (25 μm thickness). On the other side of the SLM, the acceptor phase was present. The acceptor phase was either pumped at 1 μL min−1 during extraction or kept stagnant (stop-flow). Amitriptyline, methadone, haloperidol, loperamide, and pethidine were selected as model analytes, and they were extracted from alkaline sample solution, through the SLM, and into 10 mM HCl or 100 mM HCOOH functioning as acceptor phase. Subsequently, the acceptor phase was either analyzed off-line by capillary electrophoresis for exact quantification, or on-line by UV detection or electrospray ionization mass spectrometry for time profiling of concentrations. The LPME-chip was found to be highly effective, and extraction efficiencies were in the range of 52–91%. When the flow of acceptor phase was turned off during extraction (stop-flow), analyte enrichment increased linearly with the extraction time. After 10 min as an example, amitriptyline was enriched by a factor of 42 from only 30 μL sample solution, and after 120 min amitriptyline was enriched by a factor of 500 from 320 μL sample solution. This suggested that the LPME-chip has great potentials for very efficient analyte enrichments from limited sample volumes in the future. 相似文献
120.