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41.
Elena B Lesage A Steuernagel S Böckmann A Emsley L 《Journal of the American Chemical Society》2005,127(49):17296-17302
A refocused INEPT through-bond coherence transfer technique is demonstrated for NMR of rigid organic solids and is shown to provide a valuable building block for the development of NMR correlation experiments in biological solids. The use of efficient proton homonuclear dipolar decoupling in combination with a direct spectral optimization procedure provides minimization of the transverse dephasing of coherences and leads to very efficient through-bond (1)H-(13)C INEPT transfer for crystalline organic compounds. Application of this technique to 2D heteronuclear correlation spectroscopy leads to up to a factor of 3 increase in sensitivity for a carbon-13 enriched sample in comparison to standard through-bond experiments and provides excellent selectivity for one-bond transfer. The method is demonstrated on a microcrystalline sample of the protein Crh (2 x 10.4 kDa). 相似文献
42.
Berquier Jean-Marc Nael Pascal Jupille Jacques Jacquiod Catherine 《Journal of Sol-Gel Science and Technology》2000,19(1-3):83-87
Fourier Transform Infrared transmission spectroscopy is used to characterize surfactant-templated silica films on glass. The calcination process is followed in situ and evidence for the removal of the surfactant along the Hoffman reaction is given. Once calcined, the surface of the pores of the mesoporous films is proven by deuteration experiment to be hydroxylated. Bands are attributed to isolated and hydrogen-bonded silanols. Silylation reaction with hexamethyldisilazane only occurs with isolated silanol groups. 相似文献
43.
The peroxide function of artemisinin has been activated by iron(II)-heme generated in situ from iron(III)-protoporphyrin-IX and glutathione, a biologically relevant reductant. In mild conditions, this reaction produced a high yield (85%) of heme derivatives alkylated at alpha-, beta-, and delta-meso positions by a C4-centered radical derived from artemisinin. 相似文献
44.
Top S el Hafa H Vessiéres A Huché M Vaissermann J Jaouen G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(22):5241-5249
In order to elucidate the extent to which recognition of the estrogen receptor is influenced by addition of an organometallic substituent at the 17 alpha position, modification of 17 beta-estradiol at this position was carried out by using the organometallic groups -C identical to C(eta 5-C5H4)RuCp, CH2-(eta 5-C5H4)RuCp, -C identical to C-(eta 5-C5H4)-W(CO)3(Me), -(C identical to CCHO)Co2(CO)6, and -(C identical to CCH2OH)Co2(CO)6. The relative binding affinity (RBA) values for estradiol receptor alpha showed that recognition was good (RBA between 20 and 13.5%) when the organometallic moiety was attached at the end of a rigid alkyne spacer. However, the affinity of the modified hormone for the receptor was severely reduced (RBA = 1%) for a substituent such as -CH2-(eta 5-C5H4)RuCP, in which the spacer is reduced to a single flexible sp3 carbon atom, allowing the organometallic moiety greater freedom of movement around the attachment point. The RBA values found were in agreement with results obtained from a molecular-modeling study in which 5, an organometallic hormone with a rigid spacer, or 7, a molecule with a flexible spacer, was inserted into the cavity of the recently characterized Ligand-Binding Domain of estrogen receptor alpha. 相似文献
45.
The field ionization (FI) mass spectra of n-heptanal and a series of deuterium labeled analogs have been studied, with the objectives of initiating systematic investigations of reaction mechanisms of FI produced ions and to permit comprison with those found for other ionization processes. It is now recognized that FI ions have: (a) lower average internal energies and (b) shorter residence times than similar ions generated by electron-impact (EI), and the possibility exists of H/D-randomization occuring in ions formed by desorption from the emitter, by unimolecular decomposition close to the emitter and by either ‘fast’ or ‘slow’ metastable decompositions. In this study only the peak shifts of normal ions could be utilized; accurate mass measurements of all major ions revealed elemental compositions similar to EI. A site-specific McLafferty rearrangement gave the base peak at m/e 44 ([C2H4O]+.), although the apparently complementary ion at m/e 70 ([C5H10]+.) arose in a less specific process. Ions at m/e 43 ([C3H7]+) and 71 ([C5H11]+ 80%; [C4H7O]+ 20%) were apparantly generated without significant H/D-scrambling. Of special interest was the observation of the rearrangement ion at m/e 86 ([C5H10O]+.) caused by loss of C-2 and C-3 as C2H4, as found for EI. It is concluded that at least in this system, decomposing molecular ions formed: (a) in the gas phase extremely close to the emitter and/or (b) on the emitter surface, have lifetimes sufficiently short to preclude complete H/D randomization. The results also provide evidence for common fragmentation mechanisms for heptanal molecular ions at both the low end and the high end of the energy distribution. 相似文献
46.
Bossée A Afonso C Fournier F Tasseau O Pepe C Bellier B Tabet JC 《Journal of mass spectrometry : JMS》2004,39(8):903-912
Peptide metallation with Cu2+ was explored in the negative ESI mode using an ion trap mass spectrometer. Under these conditions, the [(M-3H) + CuII]- species formed were investigated under low-energy collision-induced dissociation conditions. MS2 experiments indicate a very different behavior of CuII metallated complexes compared with [M-H]- species. CuII induces an easy loss of CO2 and specific side-chain cleavages (by radical losses) at the C-terminal residue, as observed previously by prompt 'in source' dissociation experiments. The loss of CO2 yields an unstable carbylide that leads to further dissociations involving the migration of a proton or a hydrogen radical (through the reduction of CuII). Multistage MS3 experiments were carried out to rationalize this behavior. Fragmentation pathways are proposed in order to explain the product ions observed. The side-chain radical loss at the C-terminus was demonstrated to be a consecutive process. Finally, evidence is provided that the specific side-chain cleavages can be used for the differentiation of Leu/Ile and Gln/Lys residues when they are located at the C-terminus. The existence of a zwitterionic form in the case of the anionic YGGFK-CuII complex is proposed. 相似文献
47.
Noëlle Martine Gosselet Horacio NaranjoEstelle Renard Catherine AmielBernard Sebille 《European Polymer Journal》2002,38(4):649-654
An acrylic polymer with pendent adamantyl groups was synthesized and its properties in an aqueous solution with a β-cyclodextrin (βCD) epichlorhydrin polymer examined. Viscosity properties of precursor and modified polymers show differences at low concentrations, but not at higher concentration probably due to very important hydrogen bonds which prevent the formation of intermolecular hydrophobic bonds. The association of both complementary polymers through the inclusion of adamantyl groups is evidenced by phases separation occurrence. Phase diagrams were established at two different concentrations of polymers. We have shown a maximal association of both polymers at these two concentrations, for the same ratio βCD moles/adamantyl groups: 2.4. Salt addition favors this association and displaces the two phases zone to smaller concentrations of modified polymer. Further, 4-nitrophenol can be extracted by the concentrated phase resulting from mixture of solutions of guest and host polymers, pointing out the availability of the associated phase to trap organic molecules. 相似文献
48.
The effect of conformational preference on the chiroptical properties of α-substituted succinic acids and esters 2 has been investigated using variable-temperature CD in solvents of different polarity. All available evidence indicates that when R' in 2 is alkyl or halogen, the preferred conformation is 1e with the -CH2COOR group eclipsed by the CO bond, while when R' in 2 is hydroxy, methoxy or amino, the major conformer is 1d in which the heteroatom is eclipsed by the CO bond. In both cases, conformation 1f appears to be the least favored, mainly on steric grounds. The results when R' = chloro or bromo do not support previously proposed conclusions and an alternative explanation is advanced. In the resultant octant projection (Fig, 2) it is shown that the sign of the Cotton effect for 1 will be determined by the position of the groups X and Y in the back octants, and since one of these is always H in the two favored conformations, the sign is actually determined by the position of the other group. This octant projection predicts successfully the sign of the ellipticity of the n→π* transition for any α-substituted succinic acid or ester with the appropriate substituent R', and appears to apply also to simple alkanoic acids and esters with the same substituents. 相似文献
49.
The short-time nuclear dynamics of Cu(H(2)O) is investigated using femtosecond photodetachment-photoionization spectroscopy and time-dependent quantum wave packet calculations. The Cu(H(2)O) dynamics is initiated in the electronic ground state of the complex by electron photodetachment from the Cu(-)(H(2)O) complex, where hydrogen atoms are oriented toward Cu. Several time-resolved resonant multiphoton ionization schemes are used to probe the ensuing reorientation and dissociation. Immediately following photodetachment, the neutral complex is far from its minimum energy geometry and possesses an internal energy comparable to the Cu-H(2)O dissociation energy and undergoes both large-amplitude H(2)O motion and dissociation. Dissociation is observed to occur on three distinct time scales: 0.6, 8, and 100 ps. These results are compared to the results of time-dependent J=0 wave packet calculations, propagating the initial anion vibrational wave functions on the ground-state potential of the neutral complex. An excellent agreement is obtained between the experimental results and the ionization signals derived from the calculated probability amplitudes. Related experiments and calculations are carried out on the Cu(D(2)O) complex, with results very similar to those of Cu(H(2)O). 相似文献
50.
Grandjean C Boutonnier A Guerreiro C Fournier JM Mulard LA 《The Journal of organic chemistry》2005,70(18):7123-7132
[reaction: see text] The nature of a linker used for preparing glycoconjugate vaccines is of utmost importance as it may lead to immunogenic biomolecules. We report the conjugation of carbohydrate haptens to protein carriers leading to potential vaccines using the traceless Staudinger ligation. The ligation relies on the selective transfer of a phosphane substituent to an azide to form a native amide bond in the final product upon release of an oxidized phosphane byproduct. We designed new phosphino-functionalized cross-linkers suitable for protein carrier derivatization. We evaluated their utility in preparing conjugates using both synthetic and purified bacterial carbohydrates. The use of a borane-protected phosphane which is deprotected at the time of the ligation reaction led to the best results observed thus far in terms of stability toward oxidation and reactivity. 相似文献