Separation Of Chemical Species Research Articles

Improvement of Bake-Out Prediction thanks to Realistic Species Separation

A new approach to material outgassing modelling based on chemical species separation was applied to Bake-Out modelling. The outgassing of the Scotchweld EC-9323-2 epoxy glue was first characterized experimentally, both before and after Bake-Out. Based on the former, the latter was modelled, following the classical approach on the one hand and the new approach on the other hand. The MS-based species separation of this new approach allowed measuring the emitted flux of each species individually, even during the outgassing phase. The evolution of these fluxes all along the outgassing tests, during the five classical 24 h plateaus was successfully modelled by diffusion-limited outgassing laws, while it proved inconsistent with a desorption-limited outgassing. Their modelling by diffusion laws allowed a very consistent modelling of the total mass measurements in TML and CVCMs, with a small number of chemical species of different volatilities. The effect of a preliminary Bake-Out on this outgassing was finally modelled and compared to the experimental characterization of the baked material. The modelling accuracy still remains comparable to that of the traditional modelling based on mathematical species. Yet, the realistic species separation of the new approach allows simpler assumptions on water regain (its first species) than the traditional one, which needs to assess the amount of water contained in each mathematical species. Progress in the new method should come from an improved species separation and a direct characterisation of the water flux.

Molecular Characterization of Polyimide Film and Silicone Adhesive Outgassing Using Mass Spectrometry

The prediction of contaminant levels is paramount to controlling and reducing their impact on space missions. In recent years, it has become clear that a real breakthrough could only be achieved through a change of paradigm, namely, by going beyond the classical characterization of total contaminant mass and instead characterizing the various emitted chemical species individually: both quantitatively and chemically. This paper first reviews the methodology proposed to achieve this objective and then its implementation on two examples of materials (Black Kapton® and NuSil CV4-2946) on the basis of existing ASTM-E-1559 outgassing data (Garrett, J. W., Glassford, P. M., and Steakley, J. M., “ASTM-E-1559 Method for Measuring Material Outgassing/Deposition Kinetics,” Journal of the IEST, Vol. 38, No. 1, 1995, pp. 19–28) including mass spectrometry (MS) data. We show that the thermogravimetric analysis performed on the contaminant deposits (heating at 1 K/min) allows a good enough time separation of chemical species to analyze and often identify them through their mass spectra. In turn, the knowledge of the fragments constituting their spectra allows an improved analysis of the MS data collected during the initial outgassing phase. The outgassing time profiles of each of these chemical species then tells a lot about their actual outgassing physical laws. On the two studied materials, outgassing physics were found to be consistent with Fickian or non-Fickian diffusion rather than with residence time desorption. After confirming these findings with more specific and more sensitive experiments, the door will be open to greatly improve assessments of the contaminant amounts and nature in flight through realistic multispecies physical models.

Modeling gas permeation mechanisms through 2D membranes: Comparison between a phenomenological model and extensive molecular simulations.

Two-dimensional (2D) membranes based on perforated graphene have great potential in the field of separation of chemical species for a variety of applications, including gas treatment. In addition to recent experimental studies, several works simulate the mechanisms of gas permeation through this type of membrane using molecular dynamics, but few combine different techniques to ensure that their method of choice captures all relevant mechanisms. In particular, the re-crossing mechanism leading a gas molecule that has crossed the plane of the membrane to rapidly re-cross it in the opposite direction has never been documented. In this work, we study gas permeation through a simplified 2D membrane model. We combine equilibrium and non-equilibrium molecular dynamics simulations to quantify the impact of these re-crossing mechanisms on the values of the computed transport coefficients. Using non-equilibrium simulations as reference, we show that the equilibrium simulation techniques commonly used can lead to a significant overestimation of the transport properties of the membrane. We propose a simple method to probe the re-crossing dynamics during equilibrium simulations, making it possible to compute correct values of the transport coefficient without the need for non-equilibrium simulations. Furthermore, by analyzing the phenomenology observed in the simulations, we derive an analytical formula for the permeance that takes the form of an Arrhenius law with a non-trivial temperature dependent prefactor. In excellent agreement with our simulation results, this model provides a simple theoretical framework that captures the main mechanisms involved in gas permeation through 2D membranes, including the effect of re-crossing.

Hierarchical Multi-Resolution Graph-Cuts for Water-Fat-Silicone Separation in Breast MRI.

Water-fat separation is a non-linear non-convex parameter estimation problem in magnetic resonance imaging typically solved using spatial constraints. However, there is still limited knowledge on how to separate in vivo three chemical species in the presence of magnetic field inhomogeneities. The proposed method uses multiple graph-cuts in a hierarchical multi-resolution framework to perform robust chemical species separation in the breast for subjects with and without silicone implants. Experimental results show that the proposed method can decrease the computational time for water-fat separation and perform accurate water-fat-silicone separation with only a limited number of acquired echo images at 3 T. The silicone-separated images have an improved spatial resolution and image contrast compared to conventional scans used for regular monitoring of the silicone implant's integrity.

Bio-oil collection system of low fluid adhesion that integrates condensation with the separation of chemical species

Bio-oil collection system of low fluid adhesion that integrates condensation with the separation of chemical species

PH and Design on n-Alkyl Alcohol Bulk Liquid Membranes for Improving Phenol Derivative Transport and Separation.

Regardless of the type of liquid membrane (LM) (Bulk Liquid Membranes (BLM), Supported Liquid Membranes (SLM) or Emulsion Liquid Membranes (ELM)), transport and separation of chemical species are conditioned by the operational (OP) and constructive design parameters (DP) of the permeation module. In the present study, the pH of the aqueous source phase (SP) and receiving phase (RP) of the proposed membrane system were selected as operational parameters. The mode of contacting the phases was chosen as the convective transport generator. The experiments used BLM-type membranes with spheres in free rotation as film contact elements of the aqueous phases with the membrane. The target chemical species were selected in the range of phenol derivatives (PD), 4–nitrophenol (NP), 2,4–dichlorophenol (DCP) and 2,4–dinitrophenol (DNP), all being substances of technical-economic and environmental interest. Due to their acid character, they allow the evaluation of the influence of pH as a determining operational parameter of transport and separation through a membrane consisting of n–octanol or n–decanol (n–AlcM). The comparative study performed for the transport of 4–nitrophenol (NP) showed that the module based on spheres (Ms) was more performant than the one with phase dispersion under the form of droplets (Md). The sphere material influenced the transport of 4–nitrophenol (NP). The transport module with glass spheres (Gl) was superior to the one using copper spheres (Cu), but especially with the one with steel spheres (St). In all the studied cases, the sphere-based module (Ms) had superior transport results compared to the module with droplets (Md). The extraction efficiency (EE) and the transport of 2,4–dichlorophenol (DCP) and 2,4–dinitrophenol (DNP), studied in the module with glass spheres, showed that the two phenolic derivatives could be separated by adjusting the pH of the source phase. At the acidic pH of the source phase (pH = 2), the two derivatives were extracted with good results (EE > 90%), while for pH values ranging from 4 to 6, they could be separated, with DCP having doubled separation efficiency compared to DNP. At a pH of 8 in the source phase, the extraction efficiency halved for both phenolic compounds.

Turbulent chemical-species mixing in the Venus lower atmosphere at different altitudes: a direct numerical simulation study relevant to understanding species spatial distribution

To evaluate a recent hypothesis of species stratification in the Venus lower atmosphere, a time-dependent, three-dimensional model is proposed for studying turbulent mixing of many species in the Venus lower atmosphere. This model is based on fundamental physics embedding non-equilibrium thermodynamics, the Onsager classical relationship between fluxes and forces, high-pressure transport property calculation and a real-gas equation of state. The conservation equations are self-contained, with no need for coefficients based on parametrizations to match Venus observations. The rationale for solving these equations in relatively small spatial domains at different altitudes in the Venus lower atmosphere is presented. The equations are solved in a temporal mixing layer configuration that is eminently suited to investigate turbulent mixing between two streams of different composition. The adopted simulation method is Direct Numerical Simulation (DNS). A substantial database of DNS realizations is generated for mixtures of two and seven species, with different levels of initial stratification, and at the realistic conditions of pressures and temperatures in the Venus lower atmosphere at three altitudes. High density-gradient magnitude regions (HDGM) are shown to form under initial high stratification conditions, with larger gradient values obtained at low altitudes where supercritical conditions occur. Independent of the altitude lower than 50 km, under low stratification conditions, mixing produces a more uniform spatial distribution of the density than at higher initial stratification. Under low initial stratification conditions, the influence of the minor species on the global behavior of the flow seems to be negligible. At high initial stratification conditions, differences in diffusion of various species play an important role in determining the mixture characteristics. The hypothesis of chemical species separation is discussed in the light of the present results which do not support the existence of stable species separation in the lower Venus atmosphere, independent of the number of species or the altitude.

Dynamic volumetric hyperpolarized 13 C imaging with multi-echo EPI.

To generate dynamic, volumetric maps of hyperpolarized [1-13 C]pyruvate and its metabolic products in vivo. Maps of chemical species were generated with iterative least squares (IDEAL) reconstruction from multiecho echo-planar imaging (EPI) of phantoms of thermally polarized 13 C-labeled chemicals and mice injected with hyperpolarized [1-13 C]pyruvate on a preclinical 3T scanner. The quality of the IDEAL decomposition of single-shot and multishot phantom images was evaluated using quantitative results from a simple pulse-and-acquire sequence as the gold standard. Time course and area-under-the-curve plots were created to analyze the distribution of metabolites in vivo. Improved separation of chemical species by IDEAL, evaluated by the amount of residual signal measured for chemicals not present in the phantoms, was observed as the number of EPI shots was increased from one to four. Dynamic three-dimensional metabolite maps of [1-13 C]pyruvate,[1-13 C]pyruvatehydrate, [1-13 C]lactate, [1-13 C]bicarbonate, and [1-13 C]alanine generated by IDEAL from interleaved multishot multiecho EPI of live mice were used to construct time course and area-under-the-curve graphs for the heart, kidneys, and liver, which showed good agreement with previously published results. IDEAL decomposition of multishot multiecho 13C EPI images is a simple, yet robust method for generating high-quality dynamic volumetric maps of hyperpolarized [1-13 C]pyruvate and its products in vivo and has potential applications for the assessment of multiorgan metabolic phenomena.

Dynamic 2D and 3D mapping of hyperpolarized pyruvate to lactate conversion in vivo with efficient multi-echo balanced steady-state free precession at 3 T.

The aim of this study was to acquire the transient MRI signal of hyperpolarized tracers and their metabolites efficiently, for which specialized imaging sequences are required. In this work, a multi-echo balanced steady-state free precession (me-bSSFP) sequence with Iterative Decomposition with Echo Asymmetry and Least squares estimation (IDEAL) reconstruction was implemented on a clinical 3 T positron-emission tomography/MRI system for fast 2D and 3D metabolic imaging. Simulations were conducted to obtain signal-efficient sequence protocols for the metabolic imaging of hyperpolarized biomolecules. The sequence was applied in vitro and in vivo for probing the enzymatic exchange of hyperpolarized [1-13 C]pyruvate and [1-13 C]lactate. Chemical shift resolution was achieved using a least-square, iterative chemical species separation algorithm in the reconstruction. In vitro, metabolic conversion rate measurements from me-bSSFP were compared with NMR spectroscopy and free induction decay-chemical shift imaging (FID-CSI). In vivo, a rat MAT-B-III tumor model was imaged with me-bSSFP and FID-CSI. 2D metabolite maps of [1-13 C]pyruvate and [1-13 C]lactate acquired with me-bSSFP showed the same spatial distributions as FID-CSI. The pyruvate-lactate conversion kinetics measured with me-bSSFP and NMR corresponded well. Dynamic 2D metabolite mapping with me-bSSFP enabled the acquisition of up to 420 time frames (scan time: 180-350 ms/frame) before the hyperpolarized [1-13 C]pyruvate was relaxed below noise level. 3D metabolite mapping with a large field of view (180 × 180 × 48 mm3 ) and high spatial resolution (5.6 × 5.6 × 2 mm3 ) was conducted with me-bSSFP in a scan time of 8.2 seconds. It was concluded that Me-bSSFP improves the spatial and temporal resolution for metabolic imaging of hyperpolarized [1-13 C]pyruvate and [1-13 C]lactate compared with either of the FID-CSI or EPSI methods reported at 3 T, providing new possibilities for clinical and preclinical applications.

Generalized parameter estimation in multi-echo gradient-echo-based chemical species separation.

To develop a generalized formulation for multi-echo gradient-echo-based chemical species separation for all MR signal models described by a weighted sum of complex exponentials with phases linear in the echo time. Constraints between estimation parameters in the signal model were abstracted into a matrix formulation of a generic parameter gradient. The signal model gradient was used in a parameter estimation algorithm and the Fisher information matrix. The general formulation was tested in numerical simulations and against literature and in vivo results. The proposed gradient-based parameter estimation and experimental design framework is universally applicable over the whole class of signal models using the matrix abstraction of the signal model-specific parameter constraints as input. Several previous results in magnetic-field mapping and water-fat imaging with different models could successfully be replicated with the same framework and only different input matrices. A framework for generalized parameter estimation in multi-echo gradient-echo MR signal models of multiple chemical species was developed and validated and its software version is freely available online.

Selenium Analysis and Speciation in Dietary Supplements Based on Next-Generation Selenium Ingredients.

Selenium is essential for humans and the deficit of Se requires supplementation. In addition to traditional forms such as Se salts, amino acids, or selenium-enriched yeast supplements, next-generation selenium supplements, with lower risk for excess supplementation, are emerging. These are based on selenium forms with lower toxicity, higher bioavailability, and controlled release, such as zerovalent selenium nanoparticles (SeNPs) and selenized polysaccharides (SPs). This article aims to focus on the existing analytical systems for the next-generation Se dietary supplement, providing, at the same time, an overview of the analytical methods available for the traditional forms. The next-generation dietary supplements are evaluated in comparison with the conventional/traditional ones, as well as the analysis and speciation methods that are suitable to reveal which Se forms and species are present in a dietary supplement. Knowledge gaps and further research potential in this field are highlighted. The review indicates that the methods of analysis of next-generation selenium supplements should include a step related to chemical species separation. Such a step would allow a proper characterization of the selenium forms/species, including molecular mass/dimension, and substantiates the marketing claims related to the main advantages of these new selenium ingredients.

High‐resolution 3D radial bSSFP with IDEAL

Radial trajectories facilitate high-resolution balanced steady state free precession (bSSFP) because the efficient gradients provide more time to extend the trajectory in k-space. A number of radial bSSFP methods that support fat-water separation have been developed; however, most of these methods require an environment with limited B0 inhomogeneity. In this work, high-resolution bSSFP with fat-water separation is achieved in more challenging B0 environments by combining a 3D radial trajectory with the IDEAL chemical species separation method. A method to maintain very high resolution within the timing constraints of bSSFP and IDEAL is described using a dual-pass pulse sequence. The sampling of a unique set of radial lines at each echo time is investigated as a means to circumvent the longer scan time that IDEAL incurs as a multiecho acquisition. The manifestation of undersampling artifacts in this trajectory and their effect on chemical species separation are investigated in comparison to the case in which each echo samples the same set of radial lines. This new bSSFP method achieves 0.63 mm isotropic resolution in a 5-min scan and is demonstrated in difficult in vivo imaging environments, including the breast and a knee with ACL reconstruction hardware at 1.5 T.

Spectrally resolved fully phase‐encoded three‐dimensional fast spin‐echo imaging

To develop and test the feasibility of a spectrally resolved fully phase-encoded (SR-FPE) three-dimensional fast spin-echo technique and to demonstrate its application for distortion-free imaging near metal and chemical species separation. In separate scans at 1.5 T, a hip prosthesis phantom and a sphere filled with gadolinium solution were imaged with SR-FPE and compared to conventional three-dimensional-fast spin-echo. Spectral modeling was performed on the SR-FPE data to generate the following parametric maps: species-specific signal (ρspecies), B0 field inhomogeneity, and R*2. The prosthesis phantom was also scanned using a 16-channel coil at 1.5 T. The fully sampled k-space data were retrospectively undersampled to demonstrate the feasibility of parallel imaging acceleration in all three phase-encoding directions, in combination with corner-cutting and half-Fourier sampling. Finally, SR-FPE was performed with an acetone/water/oil phantom to test chemical species separation. High quality distortion-free images and parametric maps were generated from SR-FPE. A 4 h SR-FPE scan was retrospectively accelerated to 12 min while preserving spectral information and 7.5 min without preserving spectral data. Chemical species separation was demonstrated in the acetone/water/oil phantom. This work demonstrates the feasibility of SR-FPE to perform chemical species separation and spectrally resolved imaging near metal without distortion, in scan times appropriate for the clinical setting.

Joule Heating Effect in Constant Voltage Mode Isotachophoresis in a Microchannel

Abstract Microchip ITP (isotachophoresis) is getting popularity as a preparative technique for preconcentration and separation of chemical species and/or ions in liquid phase. In constant voltage mode ITP, generally a high electric potential difference is applied to a discontinuous buffer for faster and higher resolution separation. However, the higher current from the applied electric field induces Joule heating in the buffer which modifies the mobility and diffusion coefficient of analytes in the system. This change in mobility and diffusion coefficient strongly influences the transient separation process in ITP. In this study the effect of Joule heating on separation behavior of analyte compounds has been presented in a constant voltage mode ITP where two chemical species are separated from an initial mixture. The model is based on mass, energy, and charge conservation and electroneutrality condition in the system. A set of nonlinear governing equations are solved numerically for temperature dependent properties such as diffusion coefficient, effective electrophoretic mobility, and thermal conductivity using a finite volume based model. Numerical results suggest that for temperature dependent properties of control parameters, the separation speed of analytes is significantly different from that of constant temperature case. In constant voltage mode ITP, the temperature peak forms at the location of trailing electrolyte, and its influence propagates toward the direction of band movement as separation proceeds.

Electromigration dispersion in a capillary in the presence of electro-osmotic flow

The differential migration of ions in an applied electric field is the basis for separation of chemical species by capillary electrophoresis. Axial diffusion of the concentration peak limits the separation efficiency. Electromigration dispersion is observed when the concentration of sample ions is comparable to that of the background ions. Under such conditions, the local electrical conductivity is significantly altered in the sample zone making the electric field, and therefore, the ion migration velocity concentration dependent. The resulting nonlinear wave exhibits shock like features, and, under certain simplifying assumptions, is described by Burgers' equation (S. Ghosal and Z. Chen Bull. Math. Biol. 201072, pg. 2047). In this paper, we consider the more general situation where the walls of the separation channel may have a non-zero zeta potential and are therefore able to sustain an electro-osmotic bulk flow. The main result is a one dimensional nonlinear advection diffusion equation for the area averaged concentration. This homogenized equation accounts for the Taylor-Aris dispersion resulting from the variation in the electro-osmotic slip velocity along the wall. It is shown that in a certain range of parameters, the electro-osmotic flow can actually reduce the total dispersion by delaying the formation of a concentration shock. However, if the electro-osmotic flow is sufficiently high, the total dispersion is increased because of the Taylor-Aris contribution.

Chemical species separation with simultaneous estimation of field map and T 2* using a k -space formulation

Chemical species separation techniques in image space are prone to incorporate several distortions. Some of these are signal accentuation in borders and geometrical warping from field inhomogeneity. These errors come from neglecting intraecho time variations. In this work, we present a new approach for chemical species separation in MRI with simultaneous estimation of field map and T2* decay, formulated entirely in k-space. In this approach, the time map is used to model the phase accrual from off-resonance precession and also the amplitude decay due to T2*. Our technique fits the signal model directly in k-space with the acquired data minimizing the l(2)-norm with an interior-point algorithm. Standard two dimensional gradient echo sequences in the thighs and head were used for demonstrating the technique. With this approach, we were able to obtain excellent estimation for the species, the field inhomogeneity, and T2* decay images. The results do not suffer from geometric distortions derived from the chemical shift or the field inhomogeneity. Importantly, as the T2* map is well positioned, the species signal in borders is correctly estimated. Considering intraecho time variations in a complete signal model in k-space for separating species yields superior estimation of the variables of interest when compared to existing methods.

Least‐squares chemical shift separation for 13C metabolic imaging

To describe a new least-squares chemical shift (LSCSI) method for separation of chemical species with widely spaced peaks in a sparse spectrum. The ability to account for species with multiple peaks is addressed. This method is applied to imaging of (13)C-labeled pyruvate and its metabolites alanine, pyruvate, and lactate. The method relies on a priori knowledge of the resonant frequencies of the different chemical species, as well as the relative signal from the two pyruvate peaks, one of which lies near the alanine peak. With this information a least-squares method was utilized for separation of signal from the three metabolites, facilitating tremendous reductions in the amount of data required to decompose the different chemical species. Optimization of echo spacing for maximum noise performance of the signal separation is also described. Imaging an enriched (13)C phantom at 3.0T, the LSCSI method demonstrates excellent metabolite separation, very similar to echo planar spectroscopic imaging (EPSI), while only using 1/16th as much data. This approach may be advantageous for in vivo hyperpolarized (13)C metabolic applications for reduced scan time compared with EPSI.

MRI of articular cartilage in OA: novel pulse sequences and compositional/functional markers

Osteoarthritis (OA) is a leading cause of disability worldwide. Magnetic resonance imaging (MRI), with its unique ability to image and characterize soft tissue non-invasively, has proven valuable in assessing cartilage in OA. The development of new, fast imaging methods with high contrast show promise to improve the magnetic resonance (MR) evaluation of this disease. In addition to morphologic MRI methods, MRI contrast mechanisms under development may reveal detailed information about the physiology of cartilage. It is anticipated that these and other MRI techniques will play an increasingly important role in assessing the success or failure of therapies for OA. On December 5 and 6, 2002, OMERACT (Outcome Measures in Rheumatology Clinical Trials) and OARSI (Osteoarthritis Research Society International) held a workshop in Bethesda, MD aiming at providing a state-of-the-art review of imaging outcome measures for OA of the knee to help guide scientists and pharmaceutical companies in the use of MRI in multi-site studies of OA. Applications of MRI were initially reviewed by a multidisciplinary, international panel of expert scientists and physicians from academia, the pharmaceutical industry and regulatory agencies. The findings of the panel were then presented to a wider group of participants for open discussion. The following report summarizes the results of these discussions with respect to novel MRI pulse sequences for evaluating articular cartilage of the knee in OA and notes any additional advances that have been made since.

Multicoil Dixon chemical species separation with an iterative least-squares estimation method.

This work describes a new approach to multipoint Dixon fat-water separation that is amenable to pulse sequences that require short echo time (TE) increments, such as steady-state free precession (SSFP) and fast spin-echo (FSE) imaging. Using an iterative linear least-squares method that decomposes water and fat images from source images acquired at short TE increments, images with a high signal-to-noise ratio (SNR) and uniform separation of water and fat are obtained. This algorithm extends to multicoil reconstruction with minimal additional complexity. Examples of single- and multicoil fat-water decompositions are shown from source images acquired at both 1.5T and 3.0T. Examples in the knee, ankle, pelvis, abdomen, and heart are shown, using FSE, SSFP, and spoiled gradient-echo (SPGR) pulse sequences. The algorithm was applied to systems with multiple chemical species, and an example of water-fat-silicone separation is shown. An analysis of the noise performance of this method is described, and methods to improve noise performance through multicoil acquisition and field map smoothing are discussed.

Magnetic composites for improved transport and separation of chemical species

Magnetic composites for improved transport and separation of chemical species