The aggregation of superparamagnetic iron oxide (SPIO) nanoparticles decreases the transverse nuclear magnetic resonance (NMR) relaxation time of adjacent water molecules measured by a Carr-Purcell-Meiboom-Gill (CPMG) pulse-echo sequence. This effect is commonly used to measure the concentrations of a variety of small molecules. We perform extensive Monte Carlo simulations of water diffusing around SPIO nanoparticle aggregates to determine the relationship between and details of the aggregate. We find that in the motional averaging regime scales as a power law with the number N of nanoparticles in an aggregate. The specific scaling is dependent on the fractal dimension d of the aggregates. We find for aggregates with d=2.2, a value typical of diffusion limited aggregation. We also find that in two-nanoparticle systems, is strongly dependent on the orientation of the two nanoparticles relative to the external magnetic field, which implies that it may be possible to sense the orientation of a two-nanoparticle aggregate. To optimize the sensitivity of SPIO nanoparticle sensors, we propose that it is best to have aggregates with few nanoparticles, close together, measured with long pulse-echo times. 相似文献
The structure of spherical micelles of the diblock poly(styrene-block-acrylic acid) [PS-b-PA] copolymer in water was investigated up to concentrations where the polyelectrolyte coronal layers have to shrink and/or interpenetrate in order to accommodate the micelles in the increasingly crowded volume. We obtained the partial structure factors pertaining to the core and corona density correlations with small angle neutron scattering and contrast matching in the water. The counterion structure factor was obtained with small angle x-ray scattering (SAXS) with a synchrotron radiation source. Furthermore, we have measured the flow curves and dynamic visco-elastic moduli. The functionality of the micelles is fixed with a 9 nm diameter PS core and a corona formed by around 100 PA arms. As shown by the SAXS intensities, the counterions are distributed in the coronal layer with the same density profile as the corona forming segments. Irrespective ionic strength and micelle charge, the corona shrinks with increasing packing fraction. At high charge and minimal screening conditions, the polyelectrolyte chains remain almost fully stretched and they interdigitate once the volume fraction exceeds the critical value 0.53+/-0.02. Interpenetration of the polyelectrolyte brushes also controls the fluid rheology: The viscosity increases by three orders of magnitude and the parallel frequency scaling behavior of the dynamic moduli suggests the formation of a physical gel. In excess salt, the coronal layers are less extended and they do not interpenetrate in the present concentration range. 相似文献
The dihydrogen adsorption isotherms of eight metal-organic frameworks (MOFs), measured at 77 K up to a pressure of 1 atm, have been examined for correlations with their structural features. All materials display approximately Type I isotherms with no hysteresis, and saturation was not reached for any of the materials under these conditions. Among the six isoreticular MOFs (IRMOFs) studied, the catenated materials exhibit the largest capacities on a molar basis, up to 9.8 H(2) per formula unit. The addition of functional groups (-Br, -NH(2), -C(2)H(4)-) to the phenylene links of IRMOF-1 (MOF-5), or their replacement with thieno[3,2-b]thiophene moieties in IRMOF-20, altered the adsorption behavior by a minor amount despite large variations in the pore volumes of the resulting materials. In contrast, replacement of the metal oxide units with those containing coordinatively unsaturated metal sites resulted in greater H(2) uptake. The enhanced affinities of these materials, MOF-74 and HKUST-1, were further demonstrated by calculation of the isosteric heats of adsorption, which were larger across much of the range of coverage examined, compared to those of representative IRMOFs. The results suggest that under low-loading conditions, the H(2) adsorption behavior of MOFs can be improved by imparting larger charge gradients on the metal oxide units and adjusting the link metrics to constrict the pore dimensions; however, a large pore volume is still a prerequisite feature. 相似文献
The bicyclic core of octosyl acid A has been prepared using a diastereoselective acetylide addition and 6-endo selenoetherification as key steps. A detailed study of the selenoetherification reaction and difficulties encountered in the conversion of a phenyl group to a carboxylic acid will be discussed. 相似文献
We say a 0–1 matrix A avoids a matrix P if no submatrix of A can be transformed into P by changing some ones to zeroes. We call P an m-tuple permutation matrix if P can be obtained by replacing each column of a permutation matrix with m copies of that column. In this paper, we investigate n×n matrices that avoid P and the maximum number ex(n,P) of ones that they can have. We prove a linear bound on ex(n,P) for any 2-tuple permutation matrix P, resolving a conjecture of Keszegh [B. Keszegh, On linear forbidden matrices, J. Combin. Theory Ser. A 116 (1) (2009) 232–241]. Using this result, we obtain a linear bound on ex(n,P) for any m-tuple permutation matrix P. Additionally, we demonstrate the existence of infinitely many minimal non-linear patterns, resolving another conjecture of Keszegh from the same paper. 相似文献
Using the theory of Witt vectors, we define ring structures on several well-known groups of arithmetic functions, which in another guise are formal Dirichlet series. The set of multiplicative arithmetic functions over a commutative ring R is shown to have a unique functorial ring structure for which the operation of addition is Dirichlet convolution and the operation of multiplication restricted to the completely multiplicative functions coincides with point-wise multiplication. The group of additive arithmetic functions over R also has a functorial ring structure. In analogy with the ghost homomorphism of Witt vectors, there is a functorial ring homomorphism from the ring of multiplicative functions to the ring of additive functions that is an isomorphism if R is a Q-algebra. The group of rational arithmetic functions, that is, the group generated by the completely multiplicative functions, forms a subring of the ring of multiplicative functions. The latter ring has the structure of a Bin(R)-algebra, where Bin(R) is the universal binomial ring equipped with a ring homomorphism to R. We use this algebra structure to study the order of a rational arithmetic function, as well the powersfα for α∈Bin(R) of a multiplicative arithmetic function f. For example, we prove new results about the powers of a given multiplicative arithmetic function that are rational. Finally, we apply our theory to the study of the zeta function of a scheme of finite type over Z. 相似文献
Ultraviolet organic light emitting diodes with 3,4,9,10-perylenetetracarboxylicdiimide (PTCDI) interlayer have been achieved. The emission spectrum and intensity were strongly dependent on the thickness of PTCDI interlayer, in spite of the fact that PTCDI has neither much lower HOMO nor much higher LUMO level, which is considered necessary for efficient charge blocking layers. The influence of PTCDI layer was investigated in three different device configurations and obtained results are discussed. For optimal device configuration, OLED with emission centered at 370 nm and turn-on voltage of 4.5 V is obtained. 相似文献
The performance of the pulsed-laser atom probe can be limited by both instrument and specimen factors. The experiments described in this article were designed to identify these factors so as to provide direction for further instrument and specimen development. Good agreement between voltage-pulsed and laser-pulsed data is found when the effective pulse fraction is less than 0.2 for pulsed-laser mode. Under the conditions reported in this article, the thermal tails of the peaks in the mass spectra did not show any significant change when produced with either a 10-ps or a 120-fs pulsed-laser source. Mass resolving power generally improves as the laser spot size and laser wavelength are decreased and as the specimen tip radius, specimen taper angle, and thermal diffusivity of the specimen material are increased. However, it is shown that two of the materials used in this study, aluminum and stainless steel, depend on these factors differently. A one-dimensional heat flow model is explored to explain these differences. The model correctly predicts the behavior of the aluminum samples, but breaks down for the stainless steel samples when the tip radius is large. A more accurate three-dimensional model is needed to overcome these discrepancies. 相似文献
The separation of americium(III) from europium(III) was achieved utilizing a bis-2,6-(5,6,7,8-tetrahydro-5,9,9-trimethyl-5,8-methano-1,2,4-benzotriazin-3-yl) pyridine (CA-BTP) chromatographic resin. The extraction chromatographic materials were prepared using various concentrations of CA-BTP. This new, hydrolytically stable extractant was impregnated on an inert polymeric support at 40% loading. The uptake of Am(III) and Eu(III) by this material from 0.1 to 4.0 M aqueous HNO3 solutions was measured. The resulting dry weight distribution ratios, Dw, indicated a strong preference for Am(III) with little affinity for Eu(III). These results are similar to recently reported solvent extraction studies indicating a maximum uptake of Am(III) in the 0.5–1.0 M HNO3 range. The resin preparation, performance, and characterization of the Am/Eu separation are reported herein.