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In this work we present a novel approach utilizing nuclear magnetic resonance (NMR) relaxometry to assess the structural stability of microcapsules employed as self-healing agents in advanced aerospace composites both in ambient and harsh environmental conditions. We successfully correlate the amount of the encapsulated self-healing agent with the signal intensity and confirm non-destructively the quantity of the encapsulated self-healing agent mass for the first time in the literature using 1H NMR spin-spin relaxation techniques on urea-formaldehyde (UF) microcapsules of different diameters containing an epoxy healing agent. The amount of self-healing agent is shown to increase by reducing the capsule diameter; however, the reduced shell mass renders the capsules more fragile and prone to failure. Most notably, via NMR experiments conducted during thermal cycling simulating flight conditions, we demonstrate that the microcapsule integrity under thermal fatigue varies according to their size. Especially we experimentally verify that the microcapsules with the most sensitive shells are the 147 nm and 133 nm diameter microcapsules, which are the most commonly used in self-healing systems. Finally, we were able to retrieve the same results using a portable NMR spectrometer developed in-house for in situ microcapsule testing, thus demonstrating the potential of NMR relaxometry as a powerful non-destructive evaluation tool for the microcapsule production line.
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Charge ordering phenomena in overdoped La1-xCaxMnO3 (LCMO) manganites with x>or=0.5 are generally believed to be associated with the formation of charge stripes composed of alternating Mn3+ and Mn4+ charges. However, a number of recent experiments indicate that instead of stripes the charge in these systems is spatially organized in a uniform charge density wave. At the same time theory predicts that the ground state is modulated by an incommensurate (IC) orbital and charge soliton lattice. Here, by using nuclear magnetic resonance we provide the first direct evidence that the spin ground state in overdoped LCMO manganites is IC modulated with phase solitons. At higher temperatures the solitonic superstructure is replaced by a uniform spin-density wave, subjected to coherent slow fluctuations, showing a striking similarity with slow fluctuations in the striped phase of high T{c} cuprates and nickelates.
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It is well known that water inside hydrophobic nano-channels diffuses faster than bulk water. Recent theoretical studies have shown that this enhancement depends on the size of the hydrophobic nanochannels. However, experimental evidence of this dependence is lacking. Here, by combining two-dimensional nuclear magnetic resonance diffusion-relaxation ( D - T 2 e f f ) spectroscopy in the stray field of a superconducting magnet and molecular dynamics simulations, we analyze the size dependence of water dynamics inside Carbon Nanotubes (CNTs) of different diameters ( 1.1 - 6.0 nm), in the temperature range of 265 - 305 K. Depending on the CNT diameter, the nanotube water is shown to resolve in two or more tubular components acquiring different self-diffusion coefficients. Most notably, a favorable CNT diameter range ( 3.0 - 4.5 nm) is experimentally verified for the first time, in which water molecule dynamics at the center of the CNTs exhibits distinctly non-Arrhenius behavior, characterized by ultrafast diffusion and extraordinary fragility, a result of significant importance in the efforts to understand water behavior in hydrophobic nanochannels.
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Different synthetic strategies are required for the two kinds of libraries being developed for combinatoral chemistry. Preparation of a 'focused' library involves conversion of a known synthetic route to the solid-phase or automated format, whereas generation of a 'prospecting' library is driven more by availability of input materials and considerations of structural novelty. While both types can be identified over the history of combinatorial chemistry, elaborating syntheses of novel, nonoligomeric, 'drug-like' molecules for use in prospecting libraries is a relatively recent development.
Assuntos
Química Orgânica , Fenômenos de Química OrgânicaRESUMO
Nuclear magnetic resonance (NMR) was used to determine the pore size distribution of hardened Portland cement pastes. The method is based on the well-known freezing point depression of water when confined inside the pore matrix of a material. It is demonstrated how this technique can be applied in cementitious materials to probe the microstructure of the main hydration product: the cement gel.
Assuntos
Cimentação , Materiais de Construção , Espectroscopia de Ressonância Magnética , Congelamento , Humanos , Pomadas , PorosidadeRESUMO
A ketolide was prepared from 14,15-dehydroerythromycin A by two different routes. The first approach involving oxidation of the 3-OH of 3-descladinosyl-14,15-dehydroerythromycin A 2'-O-acetate gave unexpectedly high levels of 3,11-double oxidation. This may be due to greater formation of the 9,12-hemiketal in 14,15-dehydroerythromycin A and concomitant exposure of the 11-OH group for oxidation. NMR studies of 14,15-dehydroerythromycin A support this hypothesis, revealing a 9:1 ratio of 9-ketone to 9,12-hemiketal in CDCl3 and a 1:1 ratio in CD3OD as contrasted with the corresponding tautomer ratios of 30:1 in CDCl3, and 6: 1 in CD3OD with erythromycin A. Alteration of the 13-substituent on the erythronolide A ring from ethyl to vinyl thus favors formation of the 9,12-hemiketal. A second route to the ketolides was developed based on these findings, in which the 11-OH is eliminated prior to oxidation of the 3-OH.
Assuntos
Antibacterianos/química , Antibacterianos/síntese química , Eritromicina/análogos & derivados , Antibacterianos/farmacologia , Resistência Microbiana a Medicamentos , Eritromicina/síntese química , Eritromicina/química , Bactérias Gram-Positivas/efeitos dos fármacos , Espectroscopia de Ressonância Magnética , Oxirredução , EstereoisomerismoRESUMO
The structural and magnetic properties and spin dynamics of dextran coated and uncoated γ-Fe(2)O(3) (maghemite) nanoparticles have been investigated using high resolution transmission electron microscopy (HRTEM), (57)Fe nuclear magnetic resonance (NMR), Mössbauer spectroscopy and dc magnetization measurements. The HRTEM observations indicated a well-crystallized system of ellipsoid-shaped nanoparticles, with an average size of 10 nm. The combined Mössbauer and magnetic study suggested the existence of significant interparticle interactions not only in the uncoated but also in the dextran coated nanoparticle assemblies. The zero-field NMR spectra of the nanoparticles at low temperatures are very similar to those of the bulk material, indicating the same hyperfine field values at saturation in accord with the performed Mössbauer measurements. The T(2) NMR spin-spin relaxation time of the nanoparticles has also been measured as a function of temperature and found to be two orders of magnitude shorter than that of the bulk material. It is shown that the thermal fluctuations in the longitudinal magnetization of the nanoparticles in the low temperature limit may account for the shortening and the temperature dependence of the T(2) relaxation time. Thus, the low temperature NMR results are in accord with the mechanism of collective magnetic excitations, due to the precession of the magnetization around the easy direction of the magnetization at an energy minimum, a mechanism originally proposed to interpret Mössbauer experiments in magnetic nanoparticles. The effect of the surface spins on the NMR relaxation mechanisms is also discussed.
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Dextranos/química , Compostos Férricos/química , Fenômenos Magnéticos , Microscopia Eletrônica de Transmissão , Nanopartículas/química , Espectroscopia de Ressonância Magnética , Espectroscopia de Mossbauer , Difração de Raios XRESUMO
Ultrasmall superparamagnetic iron oxide nanoparticles coated with gummic acid have been investigated as possible constituents of aqueous ferrofluids for biomedical applications and especially for MRI contrast agent. The structural characteristics and the size of the nanoparticles have been analyzed as well as the magnetic properties. In order to evaluate any possible capabilities as a contrast agent, the relaxation time, T2, of hydrogen protons in the colloidal solutions of nanoparticles have been measured in order to gain information on the relaxation behavior compared to other MRI contrast agents. The in vitro cytotoxicity of the obtained magnetic nanoparticles of iron oxide coated with gummic acid was investigated by two separate methods (MTT and FACS analysis) and by using three different normal and transformed cell lines. Our results showed that the synthesized nanoparticles had no toxic effect on any of the cell lines used.
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Novel polymer gel electrolytes have been prepared by incorporating LiI-I(2) solutions into a polyethylene oxide matrix supported by a TiO(2) filler. The gel electrolytes, based on either acetonitrile or propylene carbonate solvents are compared with liquid standard ones and are examined by (7)Li solid state nuclear magnetic resonance relaxometry and diffusion measurements. In parallel, the triiodide apparent diffusion coefficient has been determined by linear sweep voltammetry. The results are correlated with atomic force microscopic images of the electrolytes and give insight of the dynamic properties of the ions in the constrained polymer medium. Furthermore, the dissociation of the ions is estimated by relating the ionic conductivity to the ionic diffusion. As a prime application, the polymer gel electrolytes were incorporated in dye sensitized solar cells and the measured energy conversion efficiencies were successfully correlated with their morphological, diffusive and conducting properties.
Assuntos
Eletrólitos/química , Iodetos/química , Iodo/química , Lítio/química , Polietilenoglicóis/química , Fenômenos Químicos , Físico-Química , Eletroquímica , Géis/química , Íons/química , Espectroscopia de Ressonância Magnética/métodos , Sensibilidade e Especificidade , Propriedades de Superfície , Fatores de TempoRESUMO
By using nuclear magnetic resonance techniques we show that for T<30 K the La0.875Sr0.125MnO3 compound displays a nonuniform charge distribution, comprised of two interconnected Mn ion subsystems with different spin, orbital, and charge couplings. The NMR results agree very well with the two spin wave stiffness constants observed at small q values in the spin wave dispersion curves [Phys. Rev. B 67, 214430 (2003)]. This picture is probably related to a yet undetermined charge and orbital superstructure occurring in the ferromagnetic insulating state of the La0.875Sr0.125MnO3 compound.
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We report (139)La nuclear magnetic resonance in ferromagnetic and insulating (FMI) La(1-x)Ca(x)MnO(3), 0.10< or =x< or =0.20, which at low temperatures shows the formation of Mn octants with enhanced Mn-O wave function overlapping and electron-spin alignment. The rapid increase of the relaxation rates and the "wipeout" of the (139)La NMR signal intensity on heating, imply a quasistatic character for the Mn octant cells in the FMI phase, which freeze below a transition temperature T(f).
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55Mn and 139La NMR measurements on a high quality single crystal of ferromagnetic (FM) La0.80Ca0.20MnO3 demonstrate the formation of localized Mn(3+,4+) states below 70 K, accompanied by a strong cooling-rate dependent increase of certain FM neutron Bragg peaks. (55,139)(1/T(1)) spin-lattice and (139)(1/T(2)) spin-spin relaxation rates are strongly enhanced on approaching this temperature from below, signaling a genuine phase transition at T(tr) approximately 70 K. The disappearance of the FM metallic signal by applying a weak external magnetic field, the different NMR radio-frequency enhancement of the FM metallic and insulating states, and the observed finite size scaling of T(tr) with Ca (hole) doping, as observed in powder La(1-x)CaxMnO3 samples, are suggestive of freezing into an inhomogeneous FM insulating and orbitally ordered state embodying "metallic" hole-rich walls.
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55Mn NMR line shape measurements in La1-xCaxMnO3 for 0.20< or =x< or =0.50 provide experimental evidence about the existence of two distinct regions in the T-x magnetic phase diagram, where the homogeneous ferromagnetic (FM) metallic state is separated into FM metallic and FM insulating regions. These results are in agreement with recent theoretical predictions, which reveal a novel electronic phase separation in two FM states, providing orbital ordering and Jahn-Teller phonons are taken into consideration.
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The polyketides FK506 (tacrolimus) and FK520 (ascomycin) are potent immunosuppressants that function by inhibiting calcineurin phosphatase through formation of an FKBP12-FK506/520-calcineurin ternary complex. They also have calcineurin-independent neuroregenerative properties in cell culture and animal models of nervous system disorders. Based on the crystal structure of the FKBP12-FK506-calcineurin complex, we deduced that the 13- and 15-methoxy groups of FK506 or FK520 are important for inhibition of calcineurin phosphatase but not for binding to FKBP12. By genetic modification of the FK520 gene cluster, we generated 13- and 15-desmethoxy analogs of FK520 that contain hydrogen, methyl, or ethyl instead of methoxy at one or both of these positions. These analogs bind FKBP12 tightly, have decreased calcineurin phosphatase inhibition and immunosuppressive properties, and enhance neurite outgrowth in cell cultures. A representative compound was also shown to accelerate nerve regeneration and functional recovery in the rat sciatic nerve crush model.