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991.
T. P. J. Linsinger J. Pauwels H. Schimmel A. Lamberty A. M. H. van der Veen G. Schumann L. Siekmann 《Analytical and bioanalytical chemistry》2000,368(6):589-594
Uncertainties of four enzyme-CRMs that have recently been certified in a co-operation between the IRMM and the International
Federation for Clinical Chemistry were estimated. Estimation was based on the sum of the uncertainties of characterization,
homogeneity and stability. Data from the certification collaborative study were used to estimate laboratory uncertainties,
which form the basis for the uncertainty of characterization. Estimations for the uncertainty of homogeneity were derived
from classical homogeneity studies. The estimations of uncertainty of stability caused the most difficulties. Realistic uncertainties
fitting the needs of customers while being derived from measurement data based on theoretical considerations were obtained.
Received: 11 May 2000 / Revised: 21 June 2000 / Accepted: 27 June 2000 相似文献
992.
Dr. Marwa Abdelmouleh Dr. Mathieu Lalande Edith Nicol Dr. Gilles Frison Prof. Dr. Guillaume van der Rest Dr. Jean-Christophe Poully 《Chemphyschem》2021,22(12):1243-1250
These last decades, it has been widely assumed that 18-crown-6-ether (CE) plays a spectator role during the chemical processes occurring in isolated host-guest complexes between peptides or proteins and CE after activation in mass spectrometers. Our present experimental and theoretical results challenge this hypothesis by showing that CE can abstract a proton or a protonated molecule from protonated peptides after activation by collisions in argon or electron capture/transfer. Furthermore, thanks to comparison between experimental and calculated values of collision cross-sections, we demonstrate that CE can change binding site after electron transfer. We also propose detailed mechanisms for these processes. 相似文献
993.
Richard B. van Breemen LeRoy B. Martin John C. Le 《Journal of the American Society for Mass Spectrometry》1991,2(2):157-163
Although frit-fast atom bombardment (frit-FAB) and continuous-flow FAB mass spectrometry have become standard methods for the analysis of peptides and peptide mixtures, these techniques have not been applied previously to the analysis of oligonucleotides. Mobilephase composition, flow rate, and sample size were optimized for the analysis of oligonucleotides by negative ion frit-FAB mass spectrometry (a type of continuous-flow FAB mass spectrometry). With a mobile phase consisting of methanol/water/triethanolamine (80:20:0.5, v/v/w), flow injection frit-FAB analysis of oligonucleotides showed lower limits of detection compared to standard probe FAB mass spectrometry. For example, in order to obtain a signal-to-noise ratio of 3:1, 38 prnol of d(GTIAAC) were required for frit-FAB mass spectrometry and 62 pmol were required for standard probe FAB mass spectrometry. The largest difference between frit-FAB and standard probe FAB was observed for d(pC)5, for which the limit of detection by frit-FAB was approximately 11-fold lower than by standard FAB mass spectrometry. Adjustment of the mobile phase to pH 7 with trifluoroacetic acid increased the limit of detection (reduced sensitivity) a minimum of sixfold. Equimolar mixtures of two or three oligonucleotides produced deprotonated molecules in identical relative abundances whether analyzed by frit-FAB or standard probe FAB mass spectrometry. Finally, frit-FAB liquid chromatography mass spectrometry was demonstrated by separating mixtures of oligonucleotides on a β -cyclodextrin high-performance liquid chromatography column with a mobile phase containing methanol, water, and triethanolamine. 相似文献
994.
Fast Field Echo imaging: an overview and contrast calculations 总被引:1,自引:0,他引:1
Current fast imaging techniques are based on gradient echo sequences with reduced flip angle excitation pulses and very short repetition times TR. Practical T2 values may be of the order of TR or longer. In this situation, a different image contrast can be obtained, depending on details of the sequence. Four essentially different versions of the basic Fast Field Echo (FFE) sequence can be distinguished and are described systematically in this article. For these sequences, image contrast formulas are presented. Practical imaging should tolerate small field inhomogeneities. This requirement can be satisfied by only three of the four versions. Numerical simulations are used to study the influence of a modified phase alternation scheme on image contrasts of two of the remaining sequences. The results of the calculations are verified by phantom studies on a 1.5-T whole-body imager. Implications for contrast in clinical images are discussed in relation to head images obtained on the same machine. 相似文献
995.
EPR investigations of Mn2+-doped solid solutions of TSCC and TSCB were performed between 4.2 K and 300 K. The Curie temperature vs. molar fraction of bromide x is nonlinear, for x ≧ 0,75 no ferroelectric EPR-line splitting occurs. The relation between the line widths and the molar fraction of bromide is discussed by means of a simple statistical model. 相似文献
996.
G. Andrehs R. Blossfeld O. Bhme W. Sachsenrder P. Schreiter 《Crystal Research and Technology》1978,13(10):1157-1161
In comparison with the solid state synthesis from the oxide components melilites are formed from vitreous materials with added oxides at lower temperatures and with higher velocity of reaction resulting in larger and more idiomorphic crystals. The crystallization mechanism of the applied vitreous materials is important for the course of the formation of the texture during sintering depending on their chemical composition. In copper slag with polyphase composition the melilite forming reaction starts during the crystallization of pyroxene using the newly relased relictic glass phase in statu nascendi. Lateron, at higher temperatures the pyroxene also reacts with other components to form melilite. In phosphor furnace slag with stoichiometric composition the polymorphic transformation of calcium silicate (CS) is important for the formation of melilite. The change of the glass structure during the nucleation of wollastonite is the process initiating the reaction. Later at higher temperatures the polymorphic transformation of metastable pseudowollastonite accelerates the formation of melilite. It could be proved that the excess of free energy in glasses speeds up crystal forming reactions with admixture components in sintering processes. The mechanism of structural and phase change processes is reflected in the temperature dependence of reaction velocity. 相似文献
997.
J. J. Zwinselman N. M. M. Nibbering J. van der Greef M. C. Ten Noever De Brauw 《Journal of mass spectrometry : JMS》1983,18(12):525-529
The positive ion field desorption (FD) spectrum of arginine taken at the best anode temperature only contains a peak due to [M+H]+ ions. At higher emitter temperatures a considerable amount of fragmentation is induced and the [M+H NH3]+ ions become most abundant. Specific 15N labelling reveals that the eliminated ammonia molecule, exclusively, contains one of the terminal nitrogen atoms of the guanidyl group. This also applies to the ammonia loss from metastably decomposing [M+H]+ ions. The positive ion fast atom bombardment (FAB) spectrum shows more fragmentation than the FD spectrum. In contrast with the FD results, the [M+H]+ ions generated upon FAB with ion lifetimes <10−6 s eliminate both ammonia containing one of the terminal nitrogen atoms of the guanidyl group and ammonia containing the α-amino group in the ratio of 1.35, as found by 15N labelling. The metastably decomposing [M+H]+ ions, however, eliminate only the former ammonia molecule. In the negative ion FD and FAB spectra no other peak than that corresponding to the [M H]− ion is observed. Some attention has been paid to the thermal degradation of arginine on the basis of a few Curie-point pyrolysis experiments. 相似文献
998.
The solute concentration profiles around KH2PO4 crystals growing or dissoloving in stagnant aqueous solutions were studied by the schlieren method after Toepler. By this technique the thicknesses of concentration boundary layers around the crystals, formed by free convection of solution, were measured in dependence of crystal size and super (under) saturation. In the case of dissolution, theoretical estimation of the boundary layer thickness yielded a fair agreement with the observed value. For growth, the process is dominantly limited by surface kinetics, whereas volume diffusion plays a minor role. 相似文献
999.
1000.
Heinz C. Schrder 《Chemie in Unserer Zeit》1986,20(4):128-138