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61.
62.
Maxit B Giermanska J Ly I Bendejacq D Mondain-Monval O Ponsinet V 《Langmuir : the ACS journal of surfaces and colloids》2011,27(5):1990-1995
We report on the structures exhibited by two different diblock poly(styrene)-b-poly(acrylic acid) (PS-b-PAA) copolymers in water, a selective solvent. Using a combination of X-ray scattering and freeze fracture-transmission electron microscopy (FF-TEM), we show that these structures can be widely swollen while retaining their initial morphology and a high degree of long-range order. The analysis of the FF-TEM pictures also evidences the presence of water crystallites of regular size and shape within the confined water domains. We relate the growth of these crystallites to the high local ionic strength of the water swelling the PAA brushes. Moreover, the confinement of the crystallites growth shows that the swollen phases have a very robust structure, potentially useful for confining colloidal particles. 相似文献
63.
Levasseur B Gonzalez-Lopez E Rossin JA Bandosz TJ 《Langmuir : the ACS journal of surfaces and colloids》2011,27(9):5354-5365
Activated carbon was impregnated with copper salt and then exposed to reductive environment using hydrazine hydrate or heat treatment under nitrogen at 925 °C. On the obtained samples, adsorption of NO(2) was carried out at dynamic conditions at ambient temperature. The adsorbents before and after exposure to nitrogen dioxide were characterized by X-ray diffraction (XRD), thermal analysis, scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM-EDX), X-ray photoelectron spectroscopy (XPS), N(2)-sorption at -196 °C, and potentiometric titration. Copper loading improved the adsorption capacity of NO(2) as well as the retention of NO formed in the process of NO(2) reduction on the carbon surface. That improvement is linked to the presence of copper metal and its high dispersion on the surface. Even though both reduction methods lead to the reduction of copper, different reactions with the carbon surface take place. Heat treatment results in a significant percentage of metallic copper and a reduction of oxygen functional groups of the carbon matrix, whereas hydrazine, besides reduction of copper, leads to an incorporation of nitrogen. The results suggest that NO(2) mainly is converted to copper nitrates although the possibility to its reduction to N(2) is not ruled out. A high capacity on hydrazine treated samples is linked to the high dispersion of metallic copper on the surface of this carbon. 相似文献
64.
Brison J Benoit DS Muramoto S Robinson M Stayton PS Castner DG 《Surface and interface analysis : SIA》2011,43(1-2):354-357
Time of flight secondary ion mass spectrometry 2D images and molecular depth profiles of human HeLa cells treated with bromodeoxyuridine (BrdU) were acquired in the dual beam mode (Bi(3) (+) analysis beam, C(60) (+) etching beam). Several preparation protocols were investigated and were compared to a simple wash-and-dry method. The feasibility of using C(60) to clean the samples prior to imaging with Bi was also investigated quantitatively by calibrating full depth profiles of the cells using atomic force microscopy. BrdU was used as a marker for the cell nucleus, facilitating identification and localization of sub-cellular features during depth profiling. Results show that C(60) can be used to remove the surface contamination and to access different layers within the cells for 2D imaging. For a 1 nA, 10 keV C(60) (+) beam incident at 45° and rastered over a 500 × 500 μm(2) area, ~1 nm of biological material was sputtered every second. Our results show that HeLa cells were completely removed after etching with 1.3×10(15) C(60) (+) ions per cm(2), giving an average etching rate of 3.9 nm for every 10(13) C(60) per cm(2) at 10 keV and 45° incidence. 相似文献
65.
Modular natural products are biosynthesized by series of enzymes that activate, assemble, and process a nascent chain of building blocks. Adenylation domains are gatekeepers in nonribosomal peptide biosynthesis, providing the entry point for assembly of typical peptide-based natural products. We report the directed evolution of an adenylation domain based on a strategy of using a weak, promiscuous activity as a springboard for reprogramming the biosynthetic assembly line. Randomization of residues invoked in a "specificity-conferring code" and selection for a non-native substrate lead to mutant G2.1, favoring smaller amino acids with a specificity change of 10(5): a 170-fold improvement for L-alanine corresponds to a 10(3)-fold decrease for its original substrate (L-phenylalanine). These results establish directed evolution as a method to change gatekeeper domain specificity and suggest that adaptation of modules in combinatorial biosynthesis is achievable with few mutations during evolution. 相似文献
66.
Aerts A Follens LR Biermans E Bals S Van Tendeloo G Loppinet B Kirschhock CE Martens JA 《Physical chemistry chemical physics : PCCP》2011,13(10):4318-4325
Synchrotron small angle X-ray scattering (SAXS) was used to characterize silicalite-1 zeolite crystallization from TEOS/TPAOH/water clear sol. SAXS patterns were recorded over a broad range of length scales, enabling the simultaneous monitoring of nanoparticles and crystals occurring at various stages of the synthesis. A simple two-population model accurately described the patterns. Nanoparticles were modeled by polydisperse core-shell spheres and crystals by monodisperse oblate ellipsoids. These models were consistent with TEM images. The SAXS results, in conjunction with in situ light scattering, showed that nucleation of crystals occurred in a short period of time. Crystals were uniform in size and shape and became increasingly anisotropic during growth. In the presence of nanoparticles, crystal growth was fast. During crystal growth, the number of nanoparticles decreased gradually but their size was constant. These observations suggested that the nanoparticles were growth units in an aggregative crystal growth mechanism. Crystals grown in the presence of nanoparticles developed a faceted habit and intergrowths. In the final stages of growth, nanoparticles were depleted. Concurrently, the crystal growth rate decreased significantly. 相似文献
67.
Benoit Enaux Victor Granet Olivier Vermorel Corine Lacour Ludovic Thobois Vincent Dugué Thierry Poinsot 《Flow, Turbulence and Combustion》2011,86(2):153-177
This paper describes a compressible Large Eddy Simulation (LES) used to investigate cyclic variations for nonreacting flow
in an optical single cylinder engine setup. The simulated operating point is part of a large experimental database designed
to validate LES for cycle-to-cycle prediction, and constitutes a first step towards the realization of fired operating points.
The computational domain covers almost the whole experimental setup (intake and exhaust plenums, intake and exhaust ducts,
cylinder) to account for acoustic phenomena. The assessment of the computation is performed in two regions of the domain:
the intake and exhaust duct predictions are compared to the results of a Helmholtz solver and the experiment (pressure transducers
and Particle Image Velocimetry (PIV)) while the in-cylinder dynamics are compared to PIV measurements. The ability of the
developed methodology to capture the correct level of cycle-to-cycle variations is demonstrated considering in-cylinder pressure
and velocity fields predictions. Cycle-to-cycle variations in velocity are highlighted and localized using a proper orthogonal
decomposition analysis. 相似文献
68.
In this paper we consider a coupled Wave-Klein—Gordon system in 3D, and prove global regularity and modified scattering for small and smooth initial data with suitable decay at infinity. This... 相似文献
69.
González-Prieto R Fleury B Schramm F Zoppellaro G Chandrasekar R Fuhr O Lebedkin S Kappes M Ruben M 《Dalton transactions (Cambridge, England : 2003)》2011,40(29):7564-7570
Two 2,6-bispyrazolylpyridine ligands (bpp) were functionalized with pyrene moieties through linkers of different lengths. In the ligand 2,6-di(1H-pyrazol-1-yl)-4-(pyren-1-yl)pyridine (L1) the pyrene group is directly connected to the bpp moiety via a C-C single bond, while in the ligand 4-(2,6-di(1H-pyrazol-1-yl)pyridin-4-yl)benzyl-4-(pyren-1-yl)butanoate (L2) it is separated by a benzyl ester group involving a flexible butanoic chain. Subsequent complexation of Fe(II) salts revealed dramatic the influence of the nature of the pyrene substitution on the spin-transition behaviour of the resulting complexes. Thus, compound [Fe(L1)(2)](ClO(4))(2) (1) is blocked in its high spin state due to constraints caused by a strong intermolecular π-π stacking in its structure. On the other hand, the flexible chain of ligand L2 in compounds [Fe(L2)(2)](ClO(4))(2) (2) and [Fe(L2)(2)](BF(4))(2)·CH(3)CN·H(2)O (3) prevents structural constraints allowing for reversible spin transitions. Temperature-dependent studies of the photophysical properties of compound 3 do not reveal any obvious correlation between the fluorescence of the pyrene group and the spin state of the spin transition core. 相似文献
70.
Benoit Bachand Mohamed Atfani Bita Samim Sophie Lévesque Daniel Simard Xianqi Kong 《Tetrahedron letters》2007,48(49):8587-8589
A practical synthetic route to various 2-alkylpropane-1,3-sultones, the key intermediates for the preparation of 2-substituted homotaurines as analogs of tramiprosate, was developed. 相似文献