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11.
Christophe Roussel Loc Dayon Henrik Jensen Hubert H. Girault 《Journal of Electroanalytical Chemistry》2004,570(2):187-199
A series of electrogenerated selective electrophiles based on substituted benzoquinones has been characterized as tags for l-cysteine and cysteine residues in proteins. The electrophiles are generated electrochemically from the corresponding hydroquinones. It is shown from mass spectrometry analysis that the electrogenerated benzoquinone can tag the biomolecules. The rate constants pertaining to the addition of l-cysteine onto the electrogenerated benzoquinones have been determined using electrochemical techniques. The substitution patterns have been unraveled leading to the assessment of site-specific rate constants. It is shown that the rate constants are primarily dependent on the electronic nature of the substituents as expressed by the Hammett substitution constant. The apparent tagging yields observed for l-cysteine in nanospray mass spectrometry experiments do not correspond to the yields expected from the electrochemical study, as the ionisation efficiencies are highly dependent on the tag. Finally, the on-line tagging has been tested using β-lactoglobulin A and myoglobin. Based on these results, it is concluded that the tagging reaction is selective towards cysteine when it takes place in the nanospray interface. The results show that the methodology presented can be used for a rapid characterization and identification of reactive sites in biomolecules. 相似文献
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Yu. V. Belovitskaya I. V. Pekov E. R. Gobechiya N. A. Yamnova Yu. K. Kabalov N. V. Chukanov J. Schneider 《Crystallography Reports》2002,47(2):223-228
The crystal structures of two ancylite specimens from Khibiny massif (the Kola Peninsula, Russia)—ancylite-(Ce) from alkali hydrothermalites (Sr1.01Ca0.02Ba0.01)Σ1.04(Ce0.52La0.28Nd0.11Pr0.04 Sm0.01)Σ0.96(CO3)2(OH0.83F0.13)Σ0.96 · 0.9H2O and ancylite-(Ce) from carbonatites—have (Sr0.80Ca0.05Ba0.01)Σ0.86(Ce0.62La0.40Nd0.09Pr0.03) Σ1.14(CO3)2(OH0.99F0.15)Σ1.14 · 1.0H2O been refined by the Rietveld method. A focusing STOE-STADIP diffractometer with a bent Ge(111) primary monochromator was used (λ MoK α 1 radiation, 2.16° < 2θ < 54.98°; reflection number 237–437). All the computations for ancylite from alkali hydrothermalites were performed within the sp. gr. Pmc21, a = 5.0634(1) Å, b = 8.5898(1) Å, c = 7.2781(1) Å, V = 316.55(1) Å3, R wp = 1.90; the computations for ancylite from carbonatites were performed within the sp. gr. Pmcn, a = 5.0577(1) Å, b = 8.5665(2) Å, c = 7.3151(2) Å, V = 316.94(1) Å3, R wp = 2.38 in the anisotropic approximation of thermal vibrations of cations and oxygen atoms. 相似文献
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B. MacMillan M. Halse M. Schneider L. Fardy Y. H. Chui B. J. Balcom 《Applied magnetic resonance》2002,22(2):247-256
Magnetic resonance imaging has rarely been applied to rigid polymeric materials, due primarily to the strong dipolar coupling and short signal lifetimes inherent in these materials. SPRITE (single point ramped imaging withT 1 enhancement) (B. J. Balcom, R. P. MacGregor, S. D. Beyea, D. P. Green, R. L. Armstrong, T. W. Bremner: J. Magn. Reson. A123, 131–134, 1996) is particularly well suited to imaging solid materials. With SPRITE, the only requirement is thatT 2* be long enough so that the signal can be phase-encoded. The minimum phase encoding time is limited by the maximum gradient strength available and by the instrument deadtime. At present this is usually tens of microseconds and will only improve with refinements in technology. We have used the SPRITE sequence in conjunction with raising the sample temperature to obtain images of rigid polymers that have largely frustrated conventional imaging methods. This approach provides a straightforward and reliable method for imaging a class of samples that, up until now, have been very difficult to image. 相似文献
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Quantitative H–Al distances in acid sites of two zeolites with MFI and IFR framework topology were obtained by numerical simulation of 1H{27Al} rotational echo adiabatic passage double resonance (REAPDOR) experiments. A 27Al offset-dependent data set yields for each resolved 1H NMR line a corresponding nuclear electric quadrupole coupling constant of the neighboring 27Al site. This information is used for analyzing a second data set for on-resonance irradiation, where the dipolar evolution time (number of rotor cycles) was varied, to yield the 1H–27Al dipolar coupling constant. Numerical simulations indicate that the REAPDOR method does not depend significantly on the polar angles, defining the orientation of the electric field gradient tensor of 27Al with respect to the Al–H dipolar vector. In contrast, the transfer of populations in double resonance sequence is sensitive to these angles, and it can be thus used to measure them. 相似文献
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Unusual current‐voltage characteristics of single crystalline and bicrystalline La0.7Ca0.3MnO3 films
The current‐voltage characteristics of single crystalline and bicrystalline La0.7Ca0.3MnO3 films were measured and analyzed. Several epitaxial films, as well as 45° [001]‐tilt grain boundaries, display current‐voltage characteristics which are asymmetric with respect to polarity reversal of the bias current. One epitaxial film has a polarity dependent resistance of ~340kΩ and of ~670kΩ in forward and in reverse direction, respectively. 相似文献
19.
Time-resolved electron transport studies on InGaAs/GaAs-QWIPs 总被引:1,自引:0,他引:1
S. Steinkogler H. Schneider R. Rehm M. Walther P. Koidl P. Grant R. Dudek H. C. Liu 《Infrared Physics & Technology》2003,44(5-6):355-361
Due to the short internal response time, quantum-well infrared photodetectors (QWIPs) are interesting for high-speed applications such as heterodyne spectroscopy or laser pulse monitoring. We studied the photocurrent transients of InGaAs/GaAs-QWIPs after irradiation with infrared laser pulses of 250 fs duration. The excitation wavelength of about 9 μm matches the peak wavelength of the QWIP structure. The photocurrent transient consists of two different dynamical components, representing the fast photoionization in the quantum-wells and the slow injection current that compensates the remaining space charge. The investigations of the different components as a function of temperature and bias voltage were performed on a nanosecond time-scale. The experimental separation of the two photocurrent contributions allows us to determine the photoconductive gain. The Fourier transform of the photocurrent transient was compared with other experimental methods including heterodyne detection and microwave rectification. The quantitative agreement between these different measurement techniques is excellent. 相似文献
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