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Menjoge AR Kayitmazer AB Dubin PL Jaeger W Vasenkov S 《The journal of physical chemistry. B》2008,112(16):4961-4966
Proton pulsed field gradient (PFG) NMR was used to study the diffusion of poly(diallyldimethylammonium chloride) (PDADMAC) in coacervates formed from this polycation and the protein bovine serum albumin (BSA). Application of high (up to 30 T/m) magnetic field gradients in PFG NMR measurements allowed probing the diffusion of PDADMAC on a length scale of displacements as small as 100 nm in coacervates formed at different pH's and ionic strengths, i.e., conditions of varying protein-polycation interaction energy. Studies were carried out for a broad range of diffusion times and corresponding values of the mean square displacements. Several ensembles of PDADMAC polycations with different diffusivities were observed in the measured range of diffusion times. The existence of these ensembles and the pattern of their changes with increasing diffusion time support the hypothesis about the microscopic heterogeneity of PDADMAC-BSA coacervates and also provide evidence for the dynamic disintegration and reformation of dense domains. 相似文献
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A green protocol (compared to the existing methodology) for carrying out Garratt–Braverman cyclization has been developed. The method involves stirring a pre-absorbed bispropargyl sulfone/ether/sulfonamide over basic alumina. The reaction with sulfones was over within 10–15 min at room temperature whereas for the ether/sulfonamide the reaction took 6–8 h at 130 °C. The products, aryl naphthalene derivatives, are obtained by simple filtration through Celite, in excellent yields. 相似文献
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Manisha Das Dipmalya Basak Prof. Dr. Zdeněk Trávníček Dr. Ján Vančo Prof. Dr. Debashis Ray 《化学:亚洲杂志》2019,14(21):3898-3914
Simultaneous incorporation of both CoII and CoIII ions within a new thioether S‐bearing phenol‐based ligand system, H3L (2,6‐bis‐[{2‐(2‐hydroxyethylthio)ethylimino}methyl]‐4‐methylphenol) formed [Co5] aggregates [CoIICoIII4L2(μ‐OH)2(μ1,3‐O2CCH3)2](ClO4)4?H2O ( 1 ) and [CoIICoIII4L2(μ‐OH)2(μ1,3‐O2CC2H5)2](ClO4)4?H2O ( 2 ). The magnetic studies revealed axial zero‐field splitting (ZFS) parameter, D/hc=?23.6 and ?24.3 cm?1, and E/D=0.03 and 0.00, respectively for 1 and 2 . Dynamic magnetic data confirmed the complexes as SIMs with Ueff/kB=30 K ( 1 ) and 33 K ( 2 ), and τ0=9.1×10?8 s ( 1 ), and 4.3×10?8 s ( 2 ). The larger atomic radius of S compared to N gave rise to less variation in the distortion of tetrahedral geometry around central CoII centers, thus affecting the D and Ueff/kB values. Theoretical studies also support the experimental findings and reveal the origin of the anisotropy parameters. In solutions, both 1 and 2 which produce {CoIII2(μ‐L)} units, display solvent‐dependent catechol oxidation behavior toward 3,5‐di‐tert‐butylcatechol in air. The presence of an adjacent CoIII ion tends to assist the electron transfer from the substrate to the metal ion center, enhancing the catalytic oxidation rate. 相似文献
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JPC – Journal of Planar Chromatography – Modern TLC - The four new spray reagents (Benzoic acid and some of its parahaloderivatives) have been introduced. These reagents enable... 相似文献