Hyperpolarized xenon associated with ligand derivatized cryptophane-A cages has been developed as a NMR based biosensor. To optimize the detection sensitivity we describe use of xenon exchange between the caged and bulk dissolved xenon as an effective signal amplifier. This approach, somewhat analogous to 'remote detection' described recently, uses the chemical exchange to repeatedly transfer spectroscopic information from caged to bulk xenon, effectively integrating the caged signal. After an optimized integration period, the signal is read out by observation of the bulk magnetization. The spectrum of the caged xenon is reconstructed through use of a variable evolution period before transfer and Fourier analysis of the bulk signal as a function of the evolution time. 相似文献
The effect of susceptibility differences between fluid and fibers on the properties of DTI fiber phantoms was investigated. Thereto, machine-made, easily producible and inexpensive DTI fiber phantoms were constructed by winding polyamide fibers of 15 microm diameter around a circular acrylic glass spindle. The achieved fractional anisotropy was 0.78+/-0.02. It is shown by phantom measurements and Monte Carlo simulations that the transversal relaxation time T(2) strongly depends on the angle between the fibers and the B(0) field if the susceptibilities of the fibers and fluid are not identical. In the phantoms, the measured T(2) time at 3 T decreased by 60% for fibers running perpendicular to B(0). Monte Carlo simulations confirmed this result and revealed that the exact relaxation time depends strongly on the exact packing of the fibers. In the phantoms, the measured diffusion was independent of fiber orientation. Monte Carlo simulations revealed that the measured diffusion strongly depends on the exact fiber packing and that field strength and -orientation dependencies of measured diffusion may be minimal for hexagonal packing while the diffusion can be underestimated by more than 50% for cubic packing at 3 T. To overcome these effects, the susceptibilities of fibers and fluid were matched using an aqueous sodium chloride solution (83 g NaCl per kilogram of water). This enables an orientation independent and reliable use of DTI phantoms for evaluation purposes. 相似文献
Recently, the authors studied the connection between each maximal monotone operator and a family of convex functions. Each member of this family characterizes the operator and satisfies two particular inequalities.
The aim of this paper is to establish the converse of the latter fact. Namely, that every convex function satisfying those two particular inequalities is associated to a unique maximal monotone operator.
An efficient computational procedure is presented for the free vibration analysis of structures with unsymmetric geometry. The procedure is based on approximating the unsymmetric vibrational response of the structure by a linear combination of a few symmetric and antisymmetric modes (global approximation vectors), each obtained using approximately half the degrees of freedom of the original model. The three key elements of the procedure are: (a) use of mixed finite element models having independent shape functions for the internal forces (stress resultants) and generalized displacements, with the internal forces allowed to be discontinuous at interelement boundaries, (b) operator splitting, or additive decomposition of the different arrays in the governing finite element equations to delineate the contributions to the symmetric and antisymmetric response vectors, and (c) use of a reduction method through successive application of the finite element method and the classical Bubnov-Galerkin technique. The finite element method is first used to generate a few symmetric and antisymmetric global approximation response vectors. Then, the classical Bubnov-Galerkin technique is used to substantially reduce the size of the eigenvalue problem.
An initial set of global approximation vectors is selected to be a few symmetric and antisymmetric eigenvectors, and their various-order derivatives with respect to a tracing parameter identifying all the correction terms to the symmetric (and antisymmetric) eigenvectors. A modified (improved) set of approximation vectors is obtained by using the inverse iteration procedure. The effectiveness of the proposed procedure is demonstrated by means of a numerical example. 相似文献
Recent publications on pharmaceutical monitoring are increasingly covering the field of illicit drugs and lately the forensic evaluation of designing illegal analogs of lifestyle drugs like the phosphodiesterase type 5 (PDE-5) inhibitors Viagra (sildenafil), Levitra (vardenafil) and Cialis (tadalafil). Recently, the presence of all three erectile dysfunction treatment drugs has been reported in wastewaters at very low concentrations. In the environment, contaminants undergo various physical or chemical processes classified into abiotic (photolysis, hydrolysis) and biotic (biodegradation) reactions. Thus, changes in the chemical structure lead to the formation of new transformation products, which may persist in the environment or be further degraded. This study describes the photolysis of sildenafil (SDF) and its human metabolite N-demethylsildenafil (DM-SDF) under simulated solar radiation (Xenon lamp). Following chromatographic separation of the irradiated samples, eight photoproducts in the SDF samples and six photoproducts for DM-SDF were detected and characterized. The combination of ultra performance liquid chromatography-electrospray ionization-quadrupole time-of-flight-mass spectrometry (UPLC-ESI-QToF-MS), liquid chromatography-atmospheric pressure chemical ionization-triple quadrupole mass spectrometry (LC-APCI-QqQ-MS) and hydrogen/deuterium-exchange experiments allowed to propose plausible chemical structures for the photoproducts, taking into account the characteristic fragmentation patterns and the accurate mass measurements. These mass spectral data provided sound evidence for the susceptibility of the piperazine ring toward photodegradation. A gradual breakdown of this heterocyclic structure gave rise to a series of products, which in part were identical for SDF and DM-SDF. The sulfonic acid, as the formal product of sulfonamide hydrolysis, was identified as key intermediate in the photolysis pathway. In both drug/metabolite molecules, phototransformation processes taking place beyond the sulfonamide group were deemed to be of minor relevance. 相似文献
In recent years, the physical and chemical effects of ultrasound in liquid and solid media have been extensively used in food processing applications. Harnessing the physical forces generated by ultrasound, in the absence and presence of cavitation, for specific food processing applications such as emulsification, filtration, tenderisation and functionality modification have been highlighted. While some applications, such as filtration and emulsification are "mature" industrial processes, other applications, such as functionality modification, are still in their early stages of development. However, various investigations discussed suggest that ultrasonic processing of food and dairy ingredients is a potential and viable technology that will be used by many food industries in the near future. 相似文献
Sub-models of mixed linear models are considered. The independence of these sub-models leads to sufficient statistics for the parameters relevant for their densities. Using pivot variables, confidence regions are obtained as well hypothesis testing for variance components, estimable functions, and estimable vectors. In addition, to compare the estimators and the models, we present the histograms with the empirical joint densities for positive and negative parts of the estimators. The figures, for the two-dimensional charts, contain the corresponding UMVUE and are all unimodal with the UMVUE near the mode. The nearness of the estimators and the modes validates the presented methodology and allows the safe use of induced densities. A numerical example applied to real data is presented. 相似文献