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排序方式: 共有598条查询结果,搜索用时 437 毫秒
61.
Sofia Nikolaou Sérgio Hiroshi Toma Vagner Roberto de Souza Juliano B. Alves Koiti Araki Henrique Eisi Toma 《Transition Metal Chemistry》2011,36(7):775-783
The triruthenium carboxylate cluster [Ru3O(OAc)6(py)2(bpp)]+ (OAc = acetate) containing the bridging 1,3-bis(4-pyridyl)propane (bpp) ligand, and its dimeric species [{Ru3O(OAc)6(py2)}2(μ-bpp)]2+ were synthesized in order to investigate their inclusion compounds with β-cyclodextrin (β-CD). Characterization of the complexes
was carried out based on spectroscopic, electrochemical and spectroelectrochemical techniques, while the formation of inclusion
complexes was evaluated using 1H NMR/NOESY spectroscopy. Since bpp is a flexible ligand, a DFT study was carried out in order to characterize its conformational
isomers and their possible role in the host–guest chemistry with β-CD. Instead of observing the formation of inclusion compounds
with different stoichiometries, we observed the formation of 1:1 bpp/β-CD compounds in which the bpp ligand assumes different
conformations. The assembly of polymetallic rotaxane species was successfully demonstrated by monitoring the 1H NMR spectra of the monomeric cluster species in the presence of aquapentacyanoferrate(II) ions and β-CD. 相似文献
62.
Dembski S Milde M Dyrba M Schweizer S Gellermann C Klockenbring T 《Langmuir : the ACS journal of surfaces and colloids》2011,27(23):14025-14032
A novel method for the synthesis of luminescent SiO(2)/calcium phosphate (CaP):Eu(3+) core-shell nanoparticles (NPs) was developed via a sol-gel route followed by annealing at a temperature of 800 °C. The object of this study was the investigation of the effect of pH on the formation of a CaP shell around the silica core. The resulting annealed NPs exhibited an amorphous SiO(2) core and a crystalline luminescent shell. The formation of a CaP layer was possible at pH below 4.5 and above 6.5 during the coating step. The crystal structure of the shell was studied by X-ray diffraction analysis. Hydroxyapatite (HAp) and α-tricalcium phosphate were detected as crystal phases of the surrounding layer. However, NPs produced under basic conditions exhibited a higher crystallinity of the CaP layer than did samples coated at pH below 4.5. In the pH interval between 4.5 and 6.5, no shell growth but the formation of secondary NPs containing CaO and Ca(OH)(2) was observed. Furthermore, SiO(2)/CP:Eu(3+) core-shell NPs were investigated by transmission electron microscopy, dynamic light scattering, Fourier transform infrared spectroscopy, inductively coupled plasma optical emission spectrometry, and photoluminescence spectroscopy. The resulting HAp-coated NPs were successfully tested by a cell-culture-based viability assay with respect to a later application as a luminescent marker for biomedical applications. 相似文献
63.
64.
Two cyclen-derived Gd probes, [Gd-DOTAM](3+) and [Gd-DOTP](5-) (DOTAM = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetamide; DOTP = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrakis(methylenephosphonate)), were assessed as paramagnetic relaxation enhancement (PRE)-inducing probes for characterization of protein-protein interactions. Two proteins, Desulfovibrio gigas rubredoxin and Desulfovibrio gigas cytochrome c(3), were used as model partners. In a (1)H NMR titration it was shown that [Gd-DOTP](5-) binds to cytochrome c(3) near heme IV, causing pronounced PREs, characterized by line width broadenings of the heme methyl resonances at ratios as low as 0.08. A K(d) of 23 ± 1 μM was calculated based on chemical shift perturbation of selected heme methyl resonances belonging to three different heme groups, caused by allosteric effects upon [Gd-DOTP](5-) binding to cytochrome c(3) at a molar ratio of 2. The other probe, [Gd-DOTAM](3+), caused PREs on a well-defined patch near the metal center of rubredoxin (especially the patch constituted by residues D19-G23 and W37-S45, which broaden beyond detection). This effect was partially reversed for some resonances (C6-Y11, in particular) when cytochrome c(3) was added to this system. Both probes were successful in causing reversible PREs at the partner binding site, thus showing to be good probes to identify partners' binding sites and since the interaction is reversible to structurally characterize protein complexes by better defining the complex interface. 相似文献
65.
Reddy PG Chun BK Zhang HR Rachakonda S Ross BS Sofia MJ 《The Journal of organic chemistry》2011,76(10):3782-3790
PSI-352938 is a novel 2'-deoxy-2'-α-fluoro-2'-β-C-methyl 3',5'-cyclic phosphate nucleotide prodrug currently under investigation for the treatment of hepatitis C virus (HCV) infection. PSI-352938 demonstrated superior characteristics in vitro that include broad genotype coverage, superior resistance profile, and high levels of active triphosphate in vivo in the liver compared to our first and second generation nucleoside inhibitors of this class. Consequently, PSI-352938 was selected for further development and an efficient and scalable synthesis was sought to support clinical development. We report an improved, diastereoselective synthesis of a key 1'-β-nucleoside intermediate 13 via S(N)2 displacement of 1-α-bromo ribofuranose sugar 16 with the potassium salt of 6-chloro-2-amino purine and an efficient method to prepare cis-Rp cyclic phosphate (PSI-352938) in a highly stereoselective manner without any chromatographic purification. The 1-α-bromo sugar 16 was stereospecifically prepared from the corresponding 1-β-lactol in high yield under mild bromination conditions using CBr(4)/PPh(3) (Appel reaction). The desired cis-Rp 3',5'-cyclic phosphate construction was accomplished using isopropyl phosphorodichloridate readily obtained from POCl(3) and isopropyl alcohol. The base combination of Et(3)N/NMI was identified as a key factor for producing PSI-352938 as the major (>95%) diastereomer (cis-Rp) in high yield after the final cyclization step. The current route described in this article was successfully used to produce PSI-352938 on multikilogram scale. 相似文献
66.
Ciobanu M Huang KT Daguer JP Barluenga S Chaloin O Schaeffer E Mueller CG Mitchell DA Winssinger N 《Chemical communications (Cambridge, England)》2011,47(33):9321-9323
We report the synthesis of a nucleic acid-encoded carbohydrate library, its combinatorial self-assembly into 37,485 pairs and a screen against DC-SIGN leading to the identification of consensus ligand motifs. A prototypical example from the selected pairs was shown to have enhanced binding. A dendrimer incorporating the selected motifs inhibited gp120's binding to dendritic cells with higher efficiency than mannan. 相似文献
67.
Huabing Liu Lizhi Xiao Huijun Yu Xin Li Baoxin Guo Zongfu Zhang Fangrong Zong Vladimir Anferov Sofia Anferova 《Applied magnetic resonance》2013,44(5):543-552
Combination of two-dimensional nuclear magnetic resonance (2-D NMR) correlation maps and a simple three-component model are proposed here to identify the structural composition of porous media. Homogeneous magnetic field and field with constant gradient of a novel Halbach sensor are employed for respective relaxation and diffusion measurements. NMR results are compared and confirmed with independent measurements on a scanning electron microscope and by energy dispersive spectrometer methods. 相似文献
68.
Kristiane M. Van Lierde Bart Vinck Sofia De Ley Gregory Clement Paul Van Cauwenberge 《Journal of voice》2005,19(4):511-518
The main purpose of this study was to determine the vocal quality characteristics among the 45 monozygotic cotwins (MT). As the performance of the voice is related to several genetically determined anatomical and physiological factors, the authors hypothesized that the vocal characteristics and the overall vocal quality by means of the Dysphonia Severity Index (DSI) will be identical in MT. An additional objective of this study was to determine whether sex and age influence vocal similarities in MT and to compare the voice characteristics of MT with the normative data of unrelated peers. As more environmental factors influence the aging of the voice, age-related differences were expected. No sex-related differences were expected. Subjective and objective assessment techniques determined the vocal quality. No significant differences were obtained, and most comparisons resulted in significant correlation coefficients. For the acoustic parameters jitter and shimmer only, no significant correlation coefficients could be obtained. It is clear that the perceptual voice characteristics, the laryngeal aerodynamic measurements of maximum phonation time (MPT), the vocal performances, and the overall vocal quality by means of the DSI are similar in MT. These vocal characteristics are not influenced either by the subjects' age or sex and are situated within the normative range of unrelated peers. To what extent other aspects (environment, anxiety, tension, etc) might play a role in the acoustical dimensions regarding frequency and amplitude perturbation, which were in the normal range, is a subject of further research. 相似文献
69.
70.
John K. Gallos Vassiliki C. Sarli Zoe S. Massen Anastassia C. Varvogli Constantina Z. Papadoyanni Sofia D. Papaspyrou Nicolaos G. Argyropoulos 《Tetrahedron》2005,61(3):565-574
A new method for the synthesis of racemic non-proteinogenic α-amino acids has been developed, which involves (i) hetero-Diels-Alder addition of ethyl 2-nitrosoacrylate to electron rich alkenes such as enol ethers, enamines and allylsilanes, (ii) NaCNBH3 reduction of the CN bond in the oxazines thus generated, the stereochemistry of the products being controlled by epimerisation of the thermodynamically less stable isomer to the more stable one, (iii) protection of the N-H group as N-Boc and (iv) finally, N-O bond cleavage of both free and protected products to give proline or bis-homoserine derivatives, respectively. An example with concomitant reduction of the carboxylate group, resulting in the formation of the respective amino alcohol is reported. Applying this methodology to a homochiral enol ether, the protected parent d-proline was prepared in enantiomerically pure form, whereas the asymmetric synthesis of the respective bis-homoserine was unsuccessful. 相似文献