Molality as a unit of measure for expressing 1H MRS brain metabolite concentrations in vivo

Absolute concentrations of cerebral metabolite in in vivo 1H magnetic resonance spectroscopy studies (1H-MRS) are widely reported in molar units as moles per liter of tissue, or in molal units as moles per kilogram of tissue. Such measurements require external referencing or assumptions as to local water content. To reduce the scan time, avoid assumptions that may be invalid under specific pathologies, and provide a universally accessible referencing procedure, we suggest that metabolite concentrations from 1H-MRS measurements in vivo be reported in molal units as moles per kilogram of tissue water. Using internal water referencing, a two-compartment water model, a simulated brain spectrum for peak identification, and a spectroscopic bi-exponential spin-spin relaxation segmentation technique, we measured the absolute concentrations for the four common 1H brain metabolites: choline (Cho), myo-inositol (mIno), phosphocreatine + creatine (Cr), and N-acetyl-aspartate (NAA), in the hippocampal region (n = 26) and along the Sylvian fissure (n = 61) of 35 healthy adults. A stimulated echo localization method (20 ms echo time, 10 ms mixing time, 4 s repetition time) yielded metabolite concentrations, uncorrected for metabolite relaxation or contributions from macromolecule resonances, that were expectantly higher than with molar literature values. Along the Sylvian fissure the average concentrations (coefficient of variation (CV)) in mmoles/kg of tissue water were 17.6 (12%) for NAA, 14.2 (9%) for Cr, 3.6 (13%) for Cho, and 13.2 (15%) for mIno. Respective values for the hippocampal region were 15.7 (20%), 14.7 (16%), 4.6 (19%), and 17.7 (26%). The concentrations of the two regions were significantly different (p 相似文献   

pH-dependent spectral properties of para-aminobenzoic acid and its derivatives

The local environment dictates the structural and functional properties of many important chemical and biological systems. The impact of pH on the photophysical properties of a series of para-aminobenzoic acids is examined using a combination of experimental spectroscopy and quantum chemical calculations. Following photoexcitation, PABA derivatives may undergo an intramolecular charge transfer (ICT) resulting in the formation of a zwitterionic species. The thermodynamics of the excited state reaction and temperature-dependence of the radiative emission processes are evaluated through variable temperature fluorescence spectroscopy carried out in a range of aqueous buffers. Quantum chemical calculations are used to analyze structural changes with modifications at the amine position and different protonation states. The ICT is only observed in the tertiary amine, which calculations show has more sp(2) character than the primary or secondary amines. Thermodynamic analysis indicates the ICT reaction is driven by entropy.     

Simulation in manufacturing and business: A review

This paper reports the results of a review of simulation applications published within peer-reviewed literature between 1997 and 2006 to provide an up-to-date picture of the role of simulation techniques within manufacturing and business. The review is characterised by three factors: wide coverage, broad scope of the simulation techniques, and a focus on real-world applications. A structured methodology was followed to narrow down the search from around 20,000 papers to 281. Results include interesting trends and patterns. For instance, although discrete event simulation is the most popular technique, it has lower stakeholder engagement than other techniques, such as system dynamics or gaming. This is highly correlated with modelling lead time and purpose. Considering application areas, modelling is mostly used in scheduling. Finally, this review shows an increasing interest in hybrid modelling as an approach to cope with complex enterprise-wide systems.     

Calculation method for the continuum states of atomic systems

In the present work, we develop a calculational method of solving the scattering equations for spherically symmetric potentials by expanding the solutions on Coulomb functions. We utilize a multistep integration scheme together with the standard partial wave analysis in a region where the potential term dominates. The method applies to any physical problem expressed as [? ² + V(r) + k ²]ψ(r) = 0, while the extension of the method to more general scattering problems is briefly discussed. At present, we demonstrate a two-step Coulomb-fitted integration scheme by calculating the short-range scattering phase shifts for various potentials V (r).     

Constrained modeling for spectroscopic measurement of bi-exponential spin-lattice relaxation of water in vivo

The (1)H NMR water signal from spectroscopic voxels localized in gray matter contains contributions from tissue and cerebral spinal fluid (CSF). A typically weak CSF signal at short echo times makes separating the tissue and CSF spin-lattice relaxation times (T(1)) difficult, often yielding poor precision in a bi-exponential relaxation model. Simulations show that reducing the variables in the T(1) model by using known signal intensity values significantly improves the precision of the T(1) measurement. The method was validated on studies on eight healthy subjects (four males and four females, mean age 21 +/- 2 years) through a total of twenty-four spectroscopic relaxation studies. Each study included both T(1) and spin-spin relaxation (T(2)) experiments. All volumes were localized along the Sylvian fissure using a stimulated echo localization technique with a mixing time of 10 ms. The T(2) experiment consisted of 16 stimulated echo acquisitions ranging from a minimum echo time (TE) of 20 ms to a maximum of 1000 ms, with a repetition time of 12 s. All T(1) experiments consisted of 16 stimulated echo acquisition, using a homospoil saturation recovery technique with a minimum recovery time of 50 ms and a maximum 12 s. The results of the T(2) measurements provided the signal intensity values used in the bi-exponential T(1) model. The mean T(1) values when the signal intensities were constrained by the T(2) results were 1055.4 ms +/- 7.4% for tissue and 5393.5 ms +/- 59% for CSF. When the signal intensities remained free variables in the model, the mean T(1) values were 1085 ms +/- 19.4% and 5038.8 ms +/- 113.0% for tissue and CSF, respectively. The resulting improvement in precision allows the water tissue T(1) value to be included in the spectroscopic characterization of brain tissue.     

Multidimensional Analytical Techniques for Studying the Thermo-Oxidative Degradation of Impact Poly(propylene)

Summary: Impact poly(propylene) copolymers (ICPP) are complex polymer systems containing various types of ethylene-propylene copolymers as well as the majority poly(propylene) phase. In this study, multidimensional analytical techniques are applied to study the thermo-oxidative degradation of these complex materials. The combination of size exclusion chromatography (SEC) and FTIR via an LC-transform interface allows for the identification and tracking of the low molecular weight oxidized products. The degradation has a significant effect on the crystallisability of the material. DSC analysis shows that as the degradation proceeds, there is a significant decrease in the onset of the melt endotherm as well as the development of a double melt peak and peak broadening. Preparative Temperature Rising Elution Fractionation (TREF) is used to isolate the various fractions according to crystallisability during the polymer degradation. TREF-SEC and TREF-(SEC-FTIR) allows for the isolation and identification of the polymer fractions undergoing oxidative degradation. It is shown that these multidimensional analytical techniques using crystallisability in the first dimensional fractionation provide more information on the mechanism and process of oxidative degradation than traditional bulk analysis methods.     

Bayesian Model Selection for Exponential Random Graph Models via Adjusted Pseudolikelihoods

Models with intractable likelihood functions arise in areas including network analysis and spatial statistics, especially those involving Gibbs random fields. Posterior parameter estimation in these settings is termed a doubly intractable problem because both the likelihood function and the posterior distribution are intractable. The comparison of Bayesian models is often based on the statistical evidence, the integral of the un-normalized posterior distribution over the model parameters which is rarely available in closed form. For doubly intractable models, estimating the evidence adds another layer of difficulty. Consequently, the selection of the model that best describes an observed network among a collection of exponential random graph models for network analysis is a daunting task. Pseudolikelihoods offer a tractable approximation to the likelihood but should be treated with caution because they can lead to an unreasonable inference. This article specifies a method to adjust pseudolikelihoods to obtain a reasonable, yet tractable, approximation to the likelihood. This allows implementation of widely used computational methods for evidence estimation and pursuit of Bayesian model selection of exponential random graph models for the analysis of social networks. Empirical comparisons to existing methods show that our procedure yields similar evidence estimates, but at a lower computational cost. Supplementary material for this article is available online.     

Calculating dispersion interactions using maximally localized Wannier functions

We investigate a recently developed approach [P. L. Silvestrelli, Phys. Rev. Lett. 100, 053002 (2008); J. Phys. Chem. A 113, 5224 (2009)] that uses maximally localized Wannier functions to evaluate the van der Waals contribution to the total energy of a system calculated with density-functional theory. We test it on a set of atomic and molecular dimers of increasing complexity (argon, methane, ethene, benzene, phthalocyanine, and copper phthalocyanine) and demonstrate that the method, as originally proposed, has a number of shortcomings that hamper its predictive power. In order to overcome these problems, we have developed and implemented a number of improvements to the method and show that these modifications give rise to calculated binding energies and equilibrium geometries that are in closer agreement to results of quantum-chemical coupled-cluster calculations.     

Novel methodology for 3D reconstruction of carotid arteries and plaque characterization based upon magnetic resonance imaging carotid angiography data

In this study, we present a novel methodology that allows reliable segmentation of the magnetic resonance images (MRIs) for accurate fully automated three-dimensional (3D) reconstruction of the carotid arteries and semiautomated characterization of plaque type. Our approach uses active contours to detect the luminal borders in the time-of-flight images and the outer vessel wall borders in the T(1)-weighted images. The methodology incorporates the connecting components theory for the automated identification of the bifurcation region and a knowledge-based algorithm for the accurate characterization of the plaque components. The proposed segmentation method was validated in randomly selected MRI frames analyzed offline by two expert observers. The interobserver variability of the method for the lumen and outer vessel wall was -1.60%±6.70% and 0.56%±6.28%, respectively, while the Williams Index for all metrics was close to unity. The methodology implemented to identify the composition of the plaque was also validated in 591 images acquired from 24 patients. The obtained Cohen's k was 0.68 (0.60-0.76) for lipid plaques, while the time needed to process an MRI sequence for 3D reconstruction was only 30 s. The obtained results indicate that the proposed methodology allows reliable and automated detection of the luminal and vessel wall borders and fast and accurate characterization of plaque type in carotid MRI sequences. These features render the currently presented methodology a useful tool in the clinical and research arena.