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11.
Manuela Martín‐Zarco Santiago Toribio Joaquín C. García‐Martínez Julián Rodríguez‐López 《Journal of polymer science. Part A, Polymer chemistry》2009,47(23):6409-6419
A series of polyamido amine (PAMAM) dendrimers (Generations 2, 3, 4, and 6) fully functionalized at their periphery with first‐ and second‐generation poly (phenylenevinylene) (PPV) dendrons have been efficiently prepared. MALDI‐TOF mass spectrometry proved to be particularly useful for the characterization of the new hybrid dendrimers as well as for the estimation of the average number of PPV dendrons attached to the surface. The optical absorption and emission properties of these systems were studied. The materials display extremely high molar extinction coefficients and emit blue light with only slightly lower fluorescence quantum yields than the corresponding free dendrons. Self‐quenching interactions between PPV units were not observed in THF. However, the luminescence properties underwent a dramatic change when toluene was used as the solvent. The lower polarity of toluene caused shrinkage of the PAMAM structure and brought the PPV chromophores closer together, leading to self‐quenching interactions and excimer formation. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6409–6419, 2009 相似文献
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We consider a continuum percolation model on \(\mathbb {R}^d\), \(d\ge 1\). For \(t,\lambda \in (0,\infty )\) and \(d\in \{1,2,3\}\), the occupied set is given by the union of independent Brownian paths running up to time t whose initial points form a Poisson point process with intensity \(\lambda >0\). When \(d\ge 4\), the Brownian paths are replaced by Wiener sausages with radius \(r>0\). We establish that, for \(d=1\) and all choices of t, no percolation occurs, whereas for \(d\ge 2\), there is a non-trivial percolation transition in t, provided \(\lambda \) and r are chosen properly. The last statement means that \(\lambda \) has to be chosen to be strictly smaller than the critical percolation parameter for the occupied set at time zero (which is infinite when \(d\in \{2,3\}\), but finite and dependent on r when \(d\ge 4\)). We further show that for all \(d\ge 2\), the unbounded cluster in the supercritical phase is unique. Along the way a finite box criterion for non-percolation in the Boolean model is extended to radius distributions with an exponential tail. This may be of independent interest. The present paper settles the basic properties of the model and should be viewed as a springboard for finer results. 相似文献
15.
Zhang Q Kang M Peterson RD Feigon J 《Journal of the American Chemical Society》2011,133(14):5190-5193
Riboswitches regulate gene expression via specific recognition of cognate metabolites by their aptamer domains, which fold into stable conformations upon ligand binding. However, the recently reported solution and crystal structures of the Bacillus subtilis preQ(1) riboswitch aptamer show small but significant differences, suggesting that there may be conformational heterogeneity in the ligand-bound state. We present a structural and dynamic characterization of this aptamer by solution NMR spectroscopy. The aptamer-preQ(1) complex is intrinsically flexible in solution, with two regions that undergo motions on different time scales. Three residues move in concert on the micro-to-millisecond time scale and may serve as the lid of the preQ(1)-binding pocket. Several Ca(2+) ions are present in the crystal structure, one of which binds with an affinity of 47 ± 2 μM in solution to a site that is formed only upon ligand binding. Addition of Ca(2+) to the aptamer-preQ(1) complex in solution results in conformational changes that account for the differences between the solution and crystal structures. Remarkably, the Ca(2+) ions present in the crystal structure, which were proposed to be important for folding and ligand recognition, are not required for either in solution. 相似文献
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Silvia García Marcos Larriba Julián García José S. Torrecilla Francisco Rodríguez 《The Journal of chemical thermodynamics》2011,43(11):1641-1645
The (liquid + liquid) equilibrium (LLE) data for two systems containing heptane, toluene, and 1-methyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide ([mpim][Tf2N]) or 1-allyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([amim][Tf2N]) ionic liquids (ILs) were determined at T = 313.2 K and atmospheric pressure. The effect of a double bond in an alkyl side chain in the imidazolium cation was evaluated in terms of selectivity and extractive capacity. The results show a decrease of the amount of toluene and heptane dissolved in the IL with the allyl group. Thus, the distribution ratios of toluene and heptane of [mpim][Tf2N] IL are higher than those of [amim][Tf2N] IL. On the other hand, the separation factor of the [amim][Tf2N] IL increases comparing to [mpim][Tf2N] IL. The NRTL model was used to correlate satisfactorily the experimental LLE data for the two studied ternary systems. 相似文献
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The combination of lag-k autocorrelation coefficients (LCCs) and thermogravimetric analyzer (TGA) equipment is defined here as a tool to detect and quantify adulterations of extra virgin olive oil (EVOO) with refined olive (ROO), refined olive pomace (ROPO), sunflower (SO) or corn (CO) oils, when the adulterating agents concentration are less than 14%. The LCC is calculated from TGA scans of adulterated EVOO samples. Then, the standardized skewness of this coefficient has been applied to classify pure and adulterated samples of EVOO. In addition, this chaotic parameter has also been used to quantify the concentration of adulterant agents, by using successful linear correlation of LCCs and ROO, ROPO, SO or CO in 462 EVOO adulterated samples. In the case of detection, more than 82% of adulterated samples have been correctly classified. In the case of quantification of adulterant concentration, by an external validation process, the LCC/TGA approach estimates the adulterant agents concentration with a mean correlation coefficient (estimated versus real adulterant agent concentration) greater than 0.90 and a mean square error less than 4.9%. 相似文献
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Narváez-Rivas M Gallardo E Ríos JJ León-Camacho M 《Journal of chromatography. A》2011,1218(22):3453-3458
A new method for the analysis of phospholipids by normal-phase HPLC is described using a silica column. Addition of ammonia and triethylamine to a gradient based on chloroform/methanol/water promoted a good and rapid separation of phospholipid classes (20 min run). The use of an evaporative light scattering detector permitted an accurate analysis of a mixture of phospholipids. Calibration curves were linear within different range for each phospholipid class. The LOD and LOQ obtained were below 0.03 and 0.05 mg kg−1 for all cases, respectively. Besides, a new method for the separation of phospholipids from total lipids before HPLC analysis by a solid-phase extraction (SPE) with Si cartridges has been developed. This methodology gave a good recovery ranging from 97 to 117%. The method was validated with a standard mixture of phospholipids. This method has been applied to characterize the phospholipid fraction of subcutaneous fat from Iberian pig. Cardiolipin, phosphatidylethanolamine, phosphatidylinositol, phosphatidylserine, phosphatidylcholine, and sphingomyelin have been described for first time in these samples. The fatty acid composition of the different phospholipid classes and their HPLC electrospray ionization mass spectrometry have been used for characterizing the molecular species present in each one. 相似文献
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Isabel Burguete M García-Verdugo E Luis SV Restrepo JA 《Physical chemistry chemical physics : PCCP》2011,13(33):14831-14838
Crosslinked polymers containing covalently attached functional sites with chemical structures related to those present in ILs and having macroscopic properties very similar to the ones of the corresponding bulk ILs can be advantageously applied to the preparation of gold nanoparticles (AuNPs). The size and morphology of the resulting metal nanoparticles (MNPs) can be easily modulated through a proper combination of the synthetic method used for the generation of the NPs and the structural elements of the polymer. Additionally, the resulting supported AuNPs are demonstrated to be stable for at least eight months with the vials open to the atmosphere. Several synthetic methodologies have been studied, as well as different structural parameters for the functional polymers. Those include the chemical nature (anions and cations) and loading of the ionic liquid-like fragments and the morphology of the polymeric matrix. The results obtained show the potential to prepare supported AuNPs with narrow size distributions and small diameters that can have potential interest for application in different fields. 相似文献