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11.
The acid–base chemistry of some ruthenium ethyne-1,2-diyl complexes, [{Ru(CO)2(η-C5H4R)}22-CC)] (R=H, Me) has been investigated. Initial protonation of [{Ru(CO)2{η-C5H4R}}22-CC)] gave the unexpected complex cation, crystallised as the BF4 salt, [{Ru(CO)2(η-C5H4R}}33-CC)][BF4] (R=Me structurally characterised). This synthesis proved to be unreliable but subsequent, careful protonation experiments gave excellent yields of the protonated ethyne-1,2-diyl complexes, [{Ru(CO)2{η-C5H4R)}2212-CCH)](BF4) (R=Me structurally characterised) which could be deprotonated in high yield to return the starting ethyne-1,2-diyl complexes.  相似文献   
12.
The reduction of 1,10-phenanthroline-5,6-quinone(I), 5,8-quinolinequinone(II) and 6,7-dichloro-5,8-quinolinequinone(III) was investigated using cyclic voltammetry and coulometry at mercury electrodes and 50% dimethylsulfoxide+water solvent. Each compound is reduced to the corresponding hydroquinone in a diffusion-controlled, reversible two-electron process. The pH-dependence of the reversible potential indicated that the quinone forms were unprotonated, but the hydroquinones could be protonated at the heterocyclic nitrogen atom with pKa = 5.3 for I and 3.5 for III. Careful analysis of the cyclic voltammetric peak shape revealed that the difference between the standard potentials for the introduction of successive electrons, E20 ? E10, was 70 ±20, >100 and 80 ± 20 mV for I–III. Investigation of the pH-dependence of E10 and E20 showed that the pKa of the semiquinone of I was about 8.  相似文献   
13.
The role of recombinant Type‐I human collagen in the free form or forming AgNP@collagen on the photophysical and photochemical behavior of rose Bengal was analyzed. The formation of dye aggregates on the protein surface was experimentally observed and corroborated by docking calculations. The formation of such aggregates is believed to change the main oxidative mechanism from Type‐II (singlet oxygen) to Type‐I (free radical) photosensitization. Remarkably, the presence of AgNP in the form of AgNP@collagen altered the dynamics of dye triplet deactivation, effectively preventing the dye degradation and reducing the extent of protein crosslinked. Both crosslinked rHC and AgNP@collagen were able to support fibroblasts proliferation, but only the material containing silver was resistant to S. epidermidis infection.  相似文献   
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15.
Rapid surface-to-volume ratio and tortuosity measurement using Difftrain   总被引:2,自引:1,他引:1  
Analysis of diffusion measurements as a function of observation time (Delta), to calculate surface-to-volume ratios (S/V) and tortuosities (kappa), is a useful tool in the characterisation of porous media using NMR. However, using conventional pulsed field gradient (PFG) measurements, this requires long total experiment times (typically hours). Here, we show how the rapid diffusion measurement pulse sequence, Difftrain, can be used to provide the required experimental data much more rapidly (typically within minutes) with a consequential reduction in total experiment time of typically over an order of magnitude. Several novel modifications to the Difftrain pulse sequence are also presented to tailor it to this particular application; these include a variable delay between echoes (to ensure optimal echo position with respect to Delta) and a variable tip angle for the refocusing pulse (to ensure optimal use of available signal). Difftrain is applied to measure both S/V and kappa for a model glass bead pack; excellent agreement is found with both a conventional PFG measurement and with a bulk gravimetric measurement of S/V.  相似文献   
16.
Described is the development and application of a versatile semisynthetic strategy, based on a combination of sortase‐mediated coupling and tetrazine ligation chemistry, which can be exploited for the efficient incorporation of tunable functionality into chimeric recombinant proteins. To demonstrate the scope of the method, the assembly of a set of bivalent ligands, which integrate members of the epidermal growth factor (EGF) ligand family, is described. By using a series of bivalent EGFs with variable intraligand spacing, the differences in structure were correlated with the ability to bias signaling in the ErbB receptor family in a cell motility assay. Biasing away from EGFR‐HER2 dimerization with a bivalent EGF was observed to reduce cell motility in an intraligand distance‐dependent fashion, thus demonstrating the utility of the approach for acutely perturbing receptor‐mediated cell signaling pathways.  相似文献   
17.
The syntheses of p-terphenylphosphonic acid and p,p″-terphenyl-bis-phosphonic acid have been developed, and the resulting products were used to prepare layered Th(IV) and Zr(IV) phosphonates. The monoacidic terphenyl species formed a bilayered structure while the diacid created a pillared geometry. Mixed component phases were also produced. Synthesis, characterization, X-ray and thermal properties of these materials are discussed.  相似文献   
18.
We report the design and synthesis of well-defined polymers for the noncovalent oligomerization of proteins. The reported scaffolds, which were generated by atom-transfer radical polymerization (ATRP), take advantage of the well-characterized interaction between a Ni2+ complex and an oligohistidine sequence (His tag). Thus, our polymers are designed to facilitate the oligomerization of any protein possessing a His tag. We demonstrate that they can oligomerize fibroblast growth factor-8b (FGF-8b) and promote FGF-8b-mediated cell proliferation in the absence of heparin.  相似文献   
19.
We present the first results of a new search for a permanent electric dipole moment of the 199Hg atom using a UV laser. Our measurements give d(199Hg) = -(1.06+/-0.49+/-0.40)x10(-28)e cm. We interpret the result as an upper limit absolute value [d(199Hg)]<2.1x10(-28)e cm (95% C.L.), which sets new constraints on theta bar;(QCD), chromo-EDMs of the quarks, and CP violation in supersymmetric models.  相似文献   
20.
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