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21.
22.
Brunsveld L Watzke A Durek T Alexandrov K Goody RS Waldmann H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(9):2756-2772
Prenylated proteins with non-native functionalities are generally very difficult to obtain by recombinant or enzymatic means. The semisynthesis of preparative amounts of prenylated Rab guanosine triphosphatases (GTPases) from recombinant proteins and synthetic prenylated peptides depends largely on the availability of functionalised prenylated peptides corresponding to the proteins' native structure or modifications thereof. Here, we describe and compare solution-phase and solid-phase strategies for the generation of peptides corresponding to the prenylated C terminus of Rab7 GTPase. The solid-phase with utilisation of a hydrazide linker emerges as the more favourable approach. It allows a fast and practical synthesis of pure peptides and gives a high degree of flexibility in their modification. To facilitate the analysis of semisynthetic proteins, the synthesised peptides were equipped with a fluorescent group. Using the described approach, we introduced fluorophores at several different positions of the Rab7 C terminus. The position of the incorporated fluorescent groups in the peptides did not influence the protein-ligation reaction, as the generated peptides could be ligated onto thioester-tagged Rab7. However, it was found that the positioning of the fluorescent group had an influence on the functionality of the Rab7 proteins; analysis of the interaction of the semisynthetic Rab7 proteins with REP (Rab escort protein) and GDI (guanosine diphosphate dissociation inhibitor) molecules revealed that modification of the peptide side chains or of the C-terminal isoprenoid did not significantly interfere with complex formation. However, functionalisation of the C terminus was found to have an adverse effect on complex formation and stability, possibly reflecting low structural flexibility of the Rab GDI/REP molecules in the vicinity of the lipid-binding site. 相似文献
23.
Mangelings D Tanret I Matthijs N Maftouh M Massart DL Vander Heyden Y 《Electrophoresis》2005,26(4-5):818-832
The effect of five factors on the capillary electrochromatographic enantioseparation of acidic compounds was studied using an experimental design. The studied factors were pH, acetonitrile content in the mobile phase, temperature, buffer concentration, and applied voltage. These experiments allowed defining a generic separation strategy applicable on acidic compounds with chemical and structural diversity. The starting screening conditions consist of a 45 mM ammonium formate electrolyte at pH 2.9 mixed with 65% acetonitrile, an applied voltage of 15 kV, and a temperature of 25 degrees C. The screening phase occasionally can be followed by an optimization procedure. Evaluation of the proposed strategy pointed out that it allows achieving baseline resolution within a relatively short time when a beginning of separation is obtained at the starting conditions. This strategy revealed enantioselectivity for 11 compounds out of 15, of which 10 could be baseline-separated after the proposed optimization steps. 相似文献
24.
E. M. Azaroual P. Luc R. Vetter 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1992,24(2):161-164
The use of an effusive beam of titanium atoms crossed with a CW single-mode tunable dye laser has allowed the high-resolution, Doppler-free study of the isotope shifts between50Ti,48Ti and46Ti, for seven 3d
2 4s
2 a3
F
J
3d
2 4s 4p z
5
D
J
, visible transitions of Ti I. The measurements show without ambiguity the existence of a non-negligible field shift. Using the values of the nuclear radii of titanium (coming from muonic X-ray measurements), it is possible to determine the respective values of the field and mass shifts. 相似文献
25.
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27.
Gerrit L'Abbé Luc Van Meervelt Sabine Emmers Wim Dehaen Suzanne Toppet 《Journal of heterocyclic chemistry》1992,29(7):1765-1768
Structural data were obtained by X-ray crystallography for the title compounds which show that they are essentially planar and exhibit an approximately linear N2-S1-N8 arrangement. In compound 3 the separation between the sulfur atom and the pyridine nitrogen atom (2.61 Å) is larger than the Huggins constant energy distance (2.58 Å), suggesting that there is little or no bonding between them. The methylated salt 4 , on the contrary, has a closer S…N(pyridine) distance (2.19 Å) with an estimated bond dissociation energy of 6 kcal/mole. 相似文献
28.
Supercritical fluid chromatography of carbohydrates 总被引:1,自引:0,他引:1
Michel Lafosse Bernard Herbreteau Luc Morin-Allory 《Journal of chromatography. A》1996,720(1-2):61-73
Supercritical fluid chromatography (SFC) is a relatively new technique applied to polar solutes such as carbohydrates about 10 years ago. The developments in the SFC of carbohydrates are summarized and a comparison between capillary and packed column SFC is presented. High-efficiency capillary columns are suitable only for derivatized carbohydrates since various packed columns are well adapted for non derivatized mono-, di- and trisaccharides and provide complementary selectivities. 相似文献
29.
Samuel Melaku Rita Cornelis Frank Vanhaecke Richard Dams Luc Moens 《Mikrochimica acta》2005,150(3-4):225-231
A simple, sensitive and inexpensive method for the speciation of Cr(VI) and Cr(III) in river and industrial wastewater was developed, optimized and validated. Samples were collected, filtered and then chromium species were determined in the filtrate. In the filtrate, total Cr was determined directly by Graphite Furnace Atomic Absorption Spectrometry (GFAAS). A portion of the filtered sample was buffered to pH 6.4, extracted with Amberlite LA-2/MIBK and finally Cr(VI) was determined in the organic extract and Cr(III) in the aqueous phase using GFAAS. The method was evaluated by analysis of the certified reference material, CRM 544, and good accuracy was obtained. The limit of detection for Cr(VI) and Cr(tot)/Cr(III) was found to be 0.30 and 0.08 µg L−1, respectively, and a precision expressed as relative standard deviation of better than 11% was achieved for nine replicates. A number of water samples from the Tinishu Akaki River, Ethiopia, and wastewater samples from a chemical plant in Germany, were analysed. In addition to the GFAAS method, Cr(tot) was also determined using ICP-MS (in CRM 544, lyophilized water, and Tinishu Akaki River water samples) and Cr(tot) and Cr(VI) using UV-VIS spectrophotometry (in CRM 544 and industrial wastewater samples). Good agreement between the different methods was found. 相似文献
30.
Pérez J Morales D Nieto S Riera L Riera V Miguel D 《Dalton transactions (Cambridge, England : 2003)》2005,(5):884-888
Cationic complexes [Mo(eta(3)-allyl)(CO)2L3]+ (L3 = either nitrogen-donor tridentate ligand or three monodentate ligands) were prepared in high yield and under mild conditions using as precursors either the triflato complex [Mo(eta(3)-allyl)(OTf)(CO)2(NCMe)2] or the combination of the chloro complex [Mo(eta(3)-allyl)Cl(CO)2(NCMe)2] and the salt NaBAr'(4)(Ar'= 3,5-bis(trifluoromethyl)phenyl). The tridentate ligands employed were 2,2':6',2'-terpyridine (terpy) and cis,cis-1,3,5-cyclohexanetriamine (CHTA), whereas the monodentate ligands imidazole (im) and 3,5-dimethylpyrazole (dmpz) were chosen. In order to stabilize the labile intermediates, an excess of acetonitrile was used in most of the syntheses. However, the pyrazole complex was prepared through a nitrile-free route to avoid reactions at the coordinated nitrile. The solid state structures of [Mo(eta(3)-methallyl)(CO)2(terpy)]OTf (2), [Mo(eta(3)-methallyl)(CO)2(CHTA)]BAr'4 (3), [Mo(eta(3)-methallyl)(CO)2(NCMe)3]BAr'4 (4), [Mo(eta(3)-allyl)(CO)2(im)3]OTf (5) and [Mo(eta(3)-allyl)(CO)2(dmpz)3]BAr'4 (6) were determined by means of single-crystal X-ray diffraction. 相似文献