905 resultados para unified chromatography
Resumo:
Development of a unified classification system to replace four of the systems currently used in disability athletics (i.e., track and field) has been widely advocated. The definition and purpose of classification, underpinned by taxonomic principles and collectively endorsed by relevant disability sport organizations, have not been developed but are required for successful implementation of a unified system. It is posited that the International classification of functioning. disability, and health (ICF), published by the World Health Organization (2001), and current disability athletics systems are, fundamentally, classifications of the functioning and disability associated with health conditions and are highly interrelated. A rationale for basing a unified disability athletics system on ICF is established. Following taxonomic analysis of the current systems, the definition and purpose of a unified disability athletics classification are proposed and discussed. The proposed taxonomic framework and definitions have implications for other disability sport classification systems.
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An active form of the Dengue virus protease NS3 (CF40.Gly.NS3pro) was expressed in Escherichia coli. This construct consists of a critical 40 amino acid cofactor domain from NS2B fused to the N-terminal 184 amino acid protease domain of NS3 via a flexible, covalent linker (Gly(4)SerGly(4)). The recombinantly produced protein is soluble and has a hexa-histidine tag engineered at the N-terminus for ease of purification using metal affinity chromatography. However, the presence of lower molecular weight impurities after affinity chromatography indicated the need for additional purification steps. The consistent appearance of these impurities suggested that they may be the products of proteolysis and/or auto-proteolysis. The latter possibility was subsequently excluded by the observation of the same impurities in a purified, catalytically inactive form of the recombinant protease (CF40.Gly.NS3pro.SA). Further analysis indicated that these impurities may represent premature translation termination products. Regardless of their origin, they were shown to form various sized aggregates with full-length CF40.Gly.NS3pro that can be separated by size exclusion chromatography, yielding fractions of active protease of sufficient purity for crystallisation trials. The ultimate goal of these studies is to obtain a crystal structure of a catalytically active form of the Dengue virus NS3 protease for structure-based drug design. (C) 2002 Elsevier Science (USA). All rights reserved.
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Death adders (genus Acanthophis) are unique among elapid snakes in both morphology and venom composition. Despite this genus being among the most divergent of all elapids, the venom has been historically regarded as relatively quite simple. In this study, liquid chromatography/mass spectrometry (LC/MS) analysis has revealed a. much greater diversity in venom composition, including the presence of molecules of novel molecular weights that may represent a new class of venom component. Furthermore, significant variation exists between species and populations,, which allow for the LC/MS fingerprinting of each species. Mass profiling of Acanthophis venoms clearly demonstrates the effectiveness of this technique which underpins fundamental studies ranging from chemotaxonomy to drug design. Copyright (C) 2002 John Wiley Sons, Ltd.
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We studied the variation in toxin profiles of purified extracts of 10 individual specimens and two pools of ciguateric Caranx latus. High-performance liquid chromatography/mass spectrometry (HPLC/MS) identified in all individual samples at least seven Caribbean ciguatoxins (C-CTXs) comprising C-CTX-1 and its epimer C-CTX-2 ([M + H](+) m/z 1141.58), and five new C-CTX congeners with pseudo-molecular ions at m/z 1141.58, 1143.60, 1157.57, 1159.58, and 1127.57. In some samples, additional C-CTX isomers were detected with [M + H](+) ions at m/z 1141.58 (two), 1143.60 (one) and 1157.57 (two). The two low-toxic pools contained only four to six ciguatoxins. The comparison in relative proportions of four different mass classes ([M + H](+) at m/z 1141, 1143, 1157 and 1127) showed that the group at m/z 1157 increased (2-20%) with flesh toxicity. More than 80% of group m/z 1141 comprised C-CTX-1, C-CTX-2 and their isomer C-CTX-1 a whose level in this group correlated with fish toxicity. Contrary to low-toxic fishes, high-risk specimens had C-CTX-1 levels
Resumo:
This investigation re-examines theoretical aspects of the allowance for effects of thermodynamic non-ideality on the characterization of protein self-association by frontal exclusion chromatography, and thereby provides methods of analysis with greater thermodynamic rigor than those used previously. Their application is illustrated by reappraisal of published exclusion chromatography data for hemoglobin on the controlled-pore-glass matrix CPG-120. The equilibrium constant of 100/M that is obtained for dimerization of the (02 species by this means is also deduced from re-examination of published studies of concentrated hemoglobin solutions by osmotic pressure and sedimentation equilibrium methods. (C) 2003 Elsevier Science B.V. All rights reserved.
Resumo:
Viewed on a hydrodynamic scale, flames in experiments are often thin so that they may be described as gasdynamic discontinuities separating the dense cold fresh mixture from the light hot burned products. The original model of a flame as a gasdynamic discontinuity was due to Darrieus and to Landau. In addition to the fluid dynamical equations, the model consists of a flame speed relation describing the evolution of the discontinuity surface, and jump conditions across the surface which relate the fluid variables on the two sides of the surface. The Darrieus-Landau model predicts, in contrast to observations, that a uniformly propagating planar flame is absolutely unstable and that the strength of the instability grows with increasing perturbation wavenumber so that there is no high-wavenumber cutoff of the instability. The model was modified by Markstein to exhibit a high-wavenumber cutoff if a phenomenological constant in the model has an appropriate sign. Both models are postulated, rather than derived from first principles, and both ignore the flame structure, which depends on chemical kinetics and transport processes within the flame. At present, there are two models which have been derived, rather than postulated, and which are valid in two non-overlapping regions of parameter space. Sivashinsky derived a generalization of the Darrieus-Landau model which is valid for Lewis numbers (ratio of thermal diffusivity to mass diffusivity of the deficient reaction component) bounded away from unity. Matalon & Matkowsky derived a model valid for Lewis numbers close to unity. Each model has its own advantages and disadvantages. Under appropriate conditions the Matalon-Matkowsky model exhibits a high-wavenumber cutoff of the Darrieus-Landau instability. However, since the Lewis numbers considered lie too close to unity, the Matalon-Matkowsky model does not capture the pulsating instability. The Sivashinsky model does capture the pulsating instability, but does not exhibit its high-wavenumber cutoff. In this paper, we derive a model consisting of a new flame speed relation and new jump conditions, which is valid for arbitrary Lewis numbers. It captures the pulsating instability and exhibits the high-wavenumber cutoff of all instabilities. The flame speed relation includes the effect of short wavelengths, not previously considered, which leads to stabilizing transverse surface diffusion terms.
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This review summarizes the development of exclusion chromatography, also termed gel filtration, molecular-sieve chromatography and gel permeation chromatography, for the quantitative characterization of solutes and solute interactions. As well as affording a means of determining molecular mass and molecular mass distribution, the technique offers a convenient way of characterizing solute selfassociation and solute-ligand interactions in terms of reaction stoichiometry and equilibrium constant. The availability of molecular-sieve media with different selective porosities ensures that very little restriction is imposed on the size of solute amenable to study. Furthermore, access to a diverse array of assay procedures for monitoring the column eluate endows analytical exclusion chromatography with far greater flexibility than other techniques from the viewpoint of solute concentration range that can be examined. In addition to its widely recognized prowess as a means of solute separation and purification, exclusion chromatography thus also possesses considerable potential for investigating the functional roles of the purified solutes. (C) 2003 Elsevier Science B.V. All rights reserved.
Resumo:
This article reviews the progress of a personal endeavour to develop chromatography as a quantitative procedure for the determination of reaction stoichiometries and equilibrium constants governing protein interactions. As well as affording insight into an aspect of chromatography with which many protein chemists are unfamiliar, it shows the way in which minor adaptations of conventional chromatographic practices have rendered the technique one of the most powerful methods available for the characterization of interactions. That pathway towards quantification is followed from the introduction of frontal gel filtration for the study of protein self-association to the characterization of ligand binding by the biosensor variant of quantitative affinity chromatography.
Resumo:
We investigate a mechanism that generates exact solutions of scalar field cosmologies in a unified way. The procedure investigated here permits to recover almost all known solutions, and allows one to derive new solutions as well. In particular, we derive and discuss one novel solution defined in terms of the Lambert function. The solutions are organised in a classification which depends on the choice of a generating function which we have denoted by x(phi) that reflects the underlying thermodynamics of the model. We also analyse and discuss the existence of form-invariance dualities between solutions. A general way of defining the latter in an appropriate fashion for scalar fields is put forward.
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This paper presents the Direct Power Control of Three-Phase Matrix Converters (DPC-MC) operating as Unified Power Flow Controllers (UPFC). Since matrix converters allow direct AC/AC power conversion without intermediate energy storage link, the resulting UPFC has reduced volume and cost, together with higher reliability. Theoretical principles of DPC-MC method are established based on an UPFC model, together with a new direct power control approach based on sliding mode control techniques. As a result, active and reactive power can be directly controlled by selection of an appropriate switching state of matrix converter. This new direct power control approach associated to matrix converters technology guarantees decoupled active and reactive power control, zero error tracking, fast response times and timely control actions. Simulation results show good performance of the proposed system.
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This paper presents a direct power control (DPC) for three-phase matrix converters operating as unified power flow controllers (UPFCs). Matrix converters (MCs) allow the direct ac/ac power conversion without dc energy storage links; therefore, the MC-based UPFC (MC-UPFC) has reduced volume and cost, reduced capacitor power losses, together with higher reliability. Theoretical principles of direct power control (DPC) based on sliding mode control techniques are established for an MC-UPFC dynamic model including the input filter. As a result, line active and reactive power, together with ac supply reactive power, can be directly controlled by selecting an appropriate matrix converter switching state guaranteeing good steady-state and dynamic responses. Experimental results of DPC controllers for MC-UPFC show decoupled active and reactive power control, zero steady-state tracking error, and fast response times. Compared to an MC-UPFC using active and reactive power linear controllers based on a modified Venturini high-frequency PWM modulator, the experimental results of the advanced DPC-MC guarantee faster responses without overshoot and no steady-state error, presenting no cross-coupling in dynamic and steady-state responses.
Resumo:
There exist striking analogies in the behaviour of eigenvalues of Hermitian compact operators, singular values of compact operators and invariant factors of homomorphisms of modules over principal ideal domains, namely diagonalization theorems, interlacing inequalities and Courant-Fischer type formulae. Carlson and Sa [D. Carlson and E.M. Sa, Generalized minimax and interlacing inequalities, Linear Multilinear Algebra 15 (1984) pp. 77-103.] introduced an abstract structure, the s-space, where they proved unified versions of these theorems in the finite-dimensional case. We show that this unification can be done using modular lattices with Goldie dimension, which have a natural structure of s-space in the finite-dimensional case, and extend the unification to the countable-dimensional case.
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A novel high throughput and scalable unified architecture for the computation of the transform operations in video codecs for advanced standards is presented in this paper. This structure can be used as a hardware accelerator in modern embedded systems to efficiently compute all the two-dimensional 4 x 4 and 2 x 2 transforms of the H.264/AVC standard. Moreover, its highly flexible design and hardware efficiency allows it to be easily scaled in terms of performance and hardware cost to meet the specific requirements of any given video coding application. Experimental results obtained using a Xilinx Virtex-5 FPGA demonstrated the superior performance and hardware efficiency levels provided by the proposed structure, which presents a throughput per unit of area relatively higher than other similar recently published designs targeting the H.264/AVC standard. Such results also showed that, when integrated in a multi-core embedded system, this architecture provides speedup factors of about 120x concerning pure software implementations of the transform algorithms, therefore allowing the computation, in real-time, of all the above mentioned transforms for Ultra High Definition Video (UHDV) sequences (4,320 x 7,680 @ 30 fps).
Resumo:
A multiresidue gas chromatographic method for the determination of six fungicides (captan, chlorthalonil, folpet, iprodione, procymidone and vinclozolin) and one acaricide (dicofol) in still and fortified wines was developed. Solid-phase microextraction (SPME) was chosen for the extraction of the compounds from the studied matrices and tandem mass spectrometry (MS/MS) detection was used. The extraction consists in a solvent free and automated procedure and the detection is highly sensitive and selective. Good linearity was obtained with correlation coefficients of regression (R2) > 0.99 for all the compounds. Satisfactory results of repeatability and intermediate precision were obtained for most of the analytes (RSD < 20%). Recoveries from spiked wine ranged from 80.1% to 112.0%. Limits of quantification (LOQs) were considerably below the proposedmaximumresidue limits (MRLs) for these compounds in grapes and below the suggested limits for wine (MRLs/10), with the exception of captan.
Resumo:
We have developed a new method for single-drop microextraction (SDME) for the preconcentration of organochlorine pesticides (OCP) from complex matrices. It is based on the use of a silicone ring at the tip of the syringe. A 5 μL drop of n-hexane is applied to an aqueous extract containing the OCP and found to be adequate to preconcentrate the OCPs prior to analysis by GC in combination with tandem mass spectrometry. Fourteen OCP were determined using this technique in combination with programmable temperature vaporization. It is shown to have many advantages over traditional split/splitless injection. The effects of kind of organic solvent, exposure time, agitation and organic drop volume were optimized. Relative recoveries range from 59 to 117 %, with repeatabilities of <15 % (coefficient of variation) were achieved. The limits of detection range from 0.002 to 0.150 μg kg−1. The method was applied to the preconcentration of OCPs in fresh strawberry, strawberry jam, and soil.