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101.
Vlekken J D'Olieslaeger M Knuyt G Vandervorst W De Schepper L 《Journal of the American Society for Mass Spectrometry》2000,11(7):650-658
In secondary ion mass spectrometry, the detection of MCs+ clusters (with M an element of the specimen) under a Cs bombardment is frequently used for the quantification of major elements. Despite some very good results obtained by this method, some problems still remain. In order to gain some more insight into these problems, the formation mechanism of the MCs+ clusters is investigated using a Monte Carlo model. It is shown that the majority of the constituent particles of the formed clusters are initially first or second neighbor atoms at the surface and that the velocity distribution of the MCs+ clusters becomes broader and peaked at higher velocities with increasing surface binding energy of the M atom. In addition, it is demonstrated that the interaction potential between the M and Cs+ particle has no influence on the velocity distribution of the MCs+ clusters. On the other hand, the cluster formation probability, defined as the probability that a sputtered M and Cs+ particle will form a MCs+ cluster, is extremely sensitive to this interaction potential. It is also shown that the cluster formation probability decreases with increasing surface binding energy. Finally, a good correspondence is obtained between the calculated and experimental velocity distributions of MCs+ clusters sputtered from different monoatomic materials. As a consequence, the Monte Carlo model and the discussed results can be validated. 相似文献
102.
Artem Malakho Marc Dussauze Bogdan Lazoryak Frederic Adamietz 《Journal of solid state chemistry》2005,178(6):1888-1897
Crystallization of glasses with compositions (1−x)(0.95 NaPO3+0.05 Na2B4O7)+xNb2O5, x=0.4, 0.43, 0.45, 0.48 was investigated by differential scanning calorimetry and X-ray powder diffraction. Crystallization of two phases was observed in the glasses with x=0.43-0.48. First phase is a sodium niobate with the structure of tetragonal tungsten bronze () and second phase is Na4Nb8P4O32 (). The crystallization of sodium niobate is correlated with increasing of nonlinear optical efficiency reported for thermally poled glasses with x>0.4. The results of Raman spectroscopy show the formation of three-dimensional (3D) niobium oxide framework in the glasses with increase of niobium concentration. This framework is supposed to have tetragonal tungsten bronze structure and to be responsible for nonlinear optical properties of the glass. Second harmonic generation signals of as prepared and crystallized glass after thermal poling are compared. The nucleation and crystallization do not improve the NLO properties of the glasses under study. 相似文献
103.
Plumb RS Stumpf CL Gorenstein MV Castro-Perez JM Dear GJ Anthony M Sweatman BC Connor SC Haselden JN 《Rapid communications in mass spectrometry : RCM》2002,16(20):1991-1996
The application of liquid chromatography/mass spectrometry (LC/MS) followed by principal components analysis (PCA) has been successfully applied to the screening of rat urine following the administration of three candidate pharmaceuticals. With this methodology it was possible to differentiate the control samples from the dosed samples and to identify the components of the mass spectrum responsible for the separation. These data clearly show that LC/MS is a viable alternative, or complementary, technique to proton NMR for metabonomics applications in drug discovery and development. 相似文献
104.
Vanommeslaeghe K Van Alsenoy C De Proft F Martins JC Tourwé D Geerlings P 《Organic & biomolecular chemistry》2003,1(16):2951-2957
Histone deacetylase (HDAC) inhibitors have recently attracted considerable interest because of their therapeutic potential for the treatment of cell proliferative diseases. An X-ray structure of a very potent inhibitor, Trichostatin A (TSA), bound to HDLP (an HDAC analogue isolated from Aquifex aeolicus), is available. From this structure, an active site model (322 atoms), relevant for the binding of TSA and structural analogues, has been derived, and TSA has been minimized in this active site at HF 3-21G* level. The resulting conformation is in excellent accordance with the X-ray structure, and indicates a deprotonation of the hydroxamic acid in TSA by His 131. Also, a water molecule was minimized in the active site. In addition to a similar deprotonation, in accordance with a possible catalytic mechanism of HDAC as proposed by Finnin et al. (M. S. Finnin, J. R. Donigian, A. Cohen, V. M. Richon, R. A. Rifkind and P. A. Marks, Nature, 1999, 401, 188-193), a displacement of the resulting OH- ion in the active site was observed. Based on these results, the difference in energy of binding between TSA and water was calculated. The resulting value is realistic in respect to experimental binding affinities. Furthermore, the mechanism of action of the His 131-Asp 166 charge relay system was investigated. Although the Asp residue in this motif is known to substantially increase the basicity of the His residue, no proton transfer from His 131 to Asp 166 was observed on binding of TSA or water. However, in the empty protonated active site, this proton transfer does occur. 相似文献
105.
106.
The amidinoethylation of alcohols takes place by the addition of sodium alkoxides 2 (R1 = Me, Et) to the CC double bond of a variety of N,N'-substituted-propenamidines 1 (Method A). This illustrates the activation of the CC double bond by the conjugated amidine function and provides a new class of Michael acceptors for alcohols. However, this activation is poorer than with other nucleophiles or Michael acceptors. The amidinoethylation makes available 3-alkoxy-N,N'-substituted-amidines not easily accessible by other classical methods. However, it is demonstrated that the general N,N'-substituted-amidine synthesis via the nitrilium salts can also apply to nitrile compounds having an alkoxygroup present on the molecule (method B). Since the cyanoethylation of alcohols (4) is a very fast and facile reaction the method B is the preferred strategy for the synthesis of 3-alkoxy-N,N'-substituted-propanamidines 3. 相似文献
107.
Joris Van Loco Maureen Moerenhout Hedwig Beernaert 《Accreditation and quality assurance》2003,8(2):61-67
A GLP study can be performed at more than one site. This is called a multi-site study. Although, the study is performed at
different sites, it is still one study and must completely comply with the GLP principles. The fact that different activities
are conducted at different sites implies that the planning, the organization and the communication are crucial for the success
of the study. This means that all the staff involved should know their responsibilities and should have the knowledge and
skills to realize all the phases of the study according to the GLP principles. To achieve a well managed multi-site study,
several strategies for setting up such a study can be followed. This paper focuses on the responsibilities, communication,
and collaboration of the personnel, which are involved in a multi-site study. Several case studies are highlighted, and we
concluded that the basic communication triangle in a single-site GLP study between test facility management, study director,
and the quality assurance unit should be extended to the communication among test facility and test site management, study
director, principle investigator(s), and the quality assurance units at the test sites.
Introduction
Received: 14 August 2002 Accepted: 26 November 2002 相似文献
108.
A microwave-assisted click chemistry synthesis of 1,4-disubstituted 1,2,3-triazoles via a copper(I)-catalyzed three-component reaction 总被引:4,自引:0,他引:4
A microwave-assisted three-component reaction was used to prepare a series of 1,4-disubstituted-1,2,3-triazoles from corresponding alkyl halides, sodium azide, and alkynes. This procedure eliminates the need to handle organic azides, as they are generated in situ, making this already powerful click process even more user-friendly and safe. 相似文献
109.
13CT1 relaxation times for the different carbons of the sodium dodecyl sulphate chain in micellar systems have been measured, using Gd3+ as a paramagnetic relaxation reagent. The fluorescence decay of ω-(-naphthyl) dodecanoic acid, solubflized in the sodium dodecyl sulphate micelles was obtained in the presence of various amounts of counterion quencher Both series of experiments point to the occurrence of chain folding and to the fact that the terminal group can approach the Stern region of the micelle. 相似文献
110.
Mass spectrometric analysis of ceramide perturbations in brain and fibroblasts of mice and human patients with peroxisomal disorders 总被引:2,自引:0,他引:2
Pettus BJ Baes M Busman M Hannun YA Van Veldhoven PP 《Rapid communications in mass spectrometry : RCM》2004,18(14):1569-1574
In this study, the levels and composition of ceramides in brains of newborn mice lacking peroxisomes (Pex5-/-, Zellweger mice) were analyzed using normal-phase high-performance liquid chromatography/atmospheric pressure chemical ionization mass spectrometry (HPLC/APCI-MS). Total ceramide compositions were found to be comparable to that of control animals. However, a minor ceramide species, containing hexacosanoic/hexacosenoic acid as the amide fatty acid, was 9-fold increased. Also, in the sphingomyelin-derived ceramides this species was elevated. Subsequent analysis of extracts from fibroblasts of Pex5-/- mice and mice with a defective peroxisomal beta-oxidation (lacking D-specific multifunctional protein 2 (MFP2)), revealed, again, a similar rise in this particular ceramide. Further, this ceramide was elevated in human X-ALD fibroblasts as well. Whether C26:1/0-ceramide is linked to some of the pathology seen in Zellweger syndrome remains to be investigated. However, an increase in this sphingolipid can be considered as a diagnostic criterion for diseases caused by defects in peroxisome biogenesis or peroxisomal beta-oxidation. 相似文献