Fast and sensitive supercritical fluid chromatography - tandem mass spectrometry multi-class screening method for the determination of doping agents in urine.

This study shows the possibility offered by modern ultra-high performance supercritical fluid chromatography combined with tandem mass spectrometry in doping control analysis. A high throughput screening method was developed for 100 substances belonging to the challenging classes of anabolic agents, hormones and metabolic modulators, synthetic cannabinoids and glucocorticoids, which should be detected at low concentrations in urine. To selectively extract these doping agents from urine, a supported liquid extraction procedure was implemented in a 48-well plate format. At the tested concentration levels ranging from 0.5 to 5 ng/mL, the recoveries were better than 70% for 48-68% of the compounds and higher than 50% for 83-87% of the tested substances. Due to the numerous interferences related to isomers of steroids and ions produced by the loss of water in the electrospray source, the choice of SFC separation conditions was very challenging. After careful optimization, a Diol stationary phase was employed. The total analysis time for the screening assay was only 8 min, and interferences as well as susceptibility to matrix effect (ME) were minimized. With the developed method, about 70% of the compounds had relative ME within the range ±20%, at a concentration of 1 and 5 ng/mL. Finally, limits of detection achieved with the above-described strategy including 5-fold preconcentration were below 0.1 ng/mL for the majority of the tested compounds. Therefore, LODs were systematically better than the minimum required performance levels established by the World anti-doping agency, except for very few metabolites.

Using computational fluid dynamics to predict head losses in the auxiliary elements of a microirrigation sand filter

It is often assumed that total head losses in a sand filter are solely due to the filtration media and that there are analytical solutions, such as the Ergun equation, to compute them. However, total head losses are also due to auxiliary elements (inlet and outlet pipes and filter nozzles), which produce undesirable head losses because they increase energy requirements without contributing to the filtration process. In this study, ANSYS Fluent version 6.3, a commercial computational fluid dynamics (CFD) software program, was used to compute head losses in different parts of a sand filter. Six different numerical filter models of varying complexities were used to understand the hydraulic behavior of the several filter elements and their importance in total head losses. The simulation results show that 84.6% of these were caused by the sand bed and 15.4% were due to auxiliary elements (4.4% in the outlet and inlet pipes, and 11.0% in the perforated plate and nozzles). Simulation results with different models show the important role of the nozzles in the hydraulic behavior of the sand filter. The relationship between the passing area through the nozzles and the passing area through the perforated plate is an important design parameter for the reduction of total head losses. A reduced relationship caused by nozzle clogging would disproportionately increase the total head losses in the sand filter

Process intensification: From optimised flow patterns to microprocess technology

This thesis is focused on process intensification. Several significant problems and applications of this theme are covered. Process intensification is nowadays one of the most popular trends in chemical engineering and attempts have been made to develop a general, systematic methodology for intensification. This seems, however, to be very difficult, because intensified processes are often based on creativity and novel ideas. Monolith reactors and microreactors are successful examples of process intensification. They are usually multichannel devices in which a proper feed technique is important for creating even fluid distribution into the channels. Two different feed techniques were tested for monoliths. In the first technique a shower method was implemented by means of perforated plates. The second technique was a dispersion method using static mixers. Both techniques offered stable operation and uniform fluid distribution. The dispersion method enabled a wider operational range in terms of liquid superficial velocity. Using dispersion method, a volumetric gas-liquid mass transfer coefficient of 2 s-1 was reached. Flow patterns play a significant role in terms of the mixing performance of micromixers. Although the geometry of a T-mixer is simple, channel configurations and dimensions had a clear effect on mixing efficiency. The flow in the microchannel was laminar, but the formation of vortices promoted mixing in micro T-mixers. The generation of vortices was dependent on the channel dimensions, configurations and flow rate. Microreactors offer a high ratio of surface area to volume. Surface forces and interactions between fluids and surfaces are, therefore, often dominant factors. In certain cases, the interactions can be effectively utilised. Different wetting properties of solid materials (PTFE and stainless steel) were applied in the separation of immiscible liquid phases. A micro-scale plate coalescer with hydrophilic and hydrophobic surfaces was used for the continuous separation of organic and aqueous phases. Complete phase separation occurred in less than 20 seconds, whereas the separation time by settling exceeded 30 min. Fluid flows can be also intensified in suitable conditions. By adding certain additives into turbulent fluid flow, it was possible to reduce friction (drag) by 40 %. Drag reduction decreases frictional pressure drop in pipelines which leads to remarkable energy savings and decreases the size or number of pumping facilities required, e.g., in oil transport pipes. Process intensification enables operation often under more optimal conditions. The consequent cost savings from reduced use of raw materials and reduced waste lead to greater economic benefits in processing.

Threshold Selection Criteria for Quantification of Lumbosacral Cerebrospinal Fluid and Root Volumes from MRI

BACKGROUND AND PURPOSE: The high variability of CSF volumes partly explains the inconsistency of anesthetic effects, but may also be due to image analysis itself. In this study, criteria for threshold selection are anatomically defined. METHODS: T2 MR images (n = 7 cases) were analyzed using 3-dimentional software. Maximal-minimal thresholds were selected in standardized blocks of 50 slices of the dural sac ending caudally at the L5-S1 intervertebral space (caudal blocks) and middle L3 (rostral blocks). Maximal CSF thresholds: threshold value was increased until at least one voxel in a CSF area appeared unlabeled and decreased until that voxel was labeled again: this final threshold was selected. Minimal root thresholds: thresholds values that selected cauda equina root area but not adjacent gray voxels in the CSF-root interface were chosen. RESULTS: Significant differences were found between caudal and rostral thresholds. No significant differences were found between expert and nonexpert observers. Average max/min thresholds were around 1.30 but max/min CSF volumes were around 1.15. Great interindividual CSF volume variability was detected (max/min volumes 1.6-2.7). CONCLUSIONS: The estimation of a close range of CSF volumes which probably contains the real CSF volume value can be standardized and calculated prior to certain intrathecal procedures

Most of the Abundant Protein Fractions of Embryonic Cerebrospinal Fluid are Produced Out of the Brain Anlagen

The microenvironment of the central nervous system is important for neuronal function and development. During the early stages of embryo development the cephalic vesicles are filled by embryonic cerebrospinal fluid, a complex fluid containing different protein fractions, which contributes to the regulation of the survival, proliferation and neurogenesis of neuroectodermal stem cells. The protein content of embryonic cerebrospinal fluid from chick and rat embryos at the start of neurogenesis has already been determined. Most of the identified gene products are thought to be involved in the regulation of developmental processes during embryogenesis. However, due to the crucial roles played by embryonic cerebrospinal fluid during brain development, the embryological origin of the gene products it contains remains an intriguing question. According to the literature most of these products are synthesised in embryonic tissues other than the neuroepithelium. In this study we examined the embryological origin of the most abundant embryonic cerebrospinal fluid protein fractions by means of slot-blot analysis and by using several different embryonic and extraembryonic protein extracts, immunodetected with polyclonal antibodies. This first attempt to elucidate their origin is not based on the proteins identified by proteomic methods, but rather on crude protein fractions detected by SDS-PAGE analysis and to which polyclonal antibodies were specifically generated. Despite some of the limitations of this study, i.e. that one protein fraction may contain more than one gene product, and that a specific gene product may be contained in different protein fractions depending on post-translational modifications, our results show that most of the analysed protein fractions are not produced by the cephalic neuroectoderm but are rather stored in the egg reservoir; furthermore, few are produced by embryo tissues, thus indicating that they must be transported from their production or storage sites to the cephalic cavities, most probably via embryonic serum. These results raise the question as to whether the transfer of proteins from these two embryo compartments is regulated at this early developmental stage.

The influence of a certain volume of fluid in the lower tear meniscus on intraocular pressure measurements using the non-contact tonometer

Background: Intraocular pressure (IOP) is the pressure inside the eye that helps to maintain the integrity and the suitable form of the ocular globe. Precise and accurate measures of IOP are needed for the diagnosis as well as follow-up of glaucoma. In daily clinical practice, Goldmann applanation tonometer (GAT) and Non-contact tonometer (NCT) are the most common devices for measuring IOP. A close agreement between these methods has been showed, particularly in normotensive patients and a poor agreement, especially when IOP levels are above the normal range. Ophthalmologists have noticed a poor agreement between NCT and GAT, observing that by using NCT and after comparing with GAT, there is an overestimation of IOP readings, and particularly it occurs when the eyes are tearful. Previous studies investigate the effect of tears in Non-contact tonometer readings by the instillation of artificial tears, concluding in one of the studies that the variation was less than 1mmHg and not clinically significant, in contrast with another study which the increases were sadistically significant. Tear menisci are a thin strip of tear fluid located between the bulbar conjunctiva and the eyelid margins. We think that the overestimation of IOP readings using NCT could be due to the presence of a higher volume of tear in the lower tear meniscus which might cause an optical interference in the optoelectronic applanation monitoring system of this deviceObjectives: To research the influence of a certain volume of fluid in the lower tear meniscus on IOP measurements using the NCT in healthy eyes. Moreover, to investigate the agreement between IOP readings obtained by NCT and GAT in the presence and absence of this volume of fluidMethods: The study design will be transversal for diagnostic tests of repeated measures. We will study patients with no ocular pathology and IOP<21mmHg. It will consist in the measurement of IOP using NCT before and after the instillation of COLIRCUSÍ FLUOTEST, used as a volume of fluid in the lower tear meniscus, to observe if there will be differences using the paired t-test. Moreover, we will take IOP measures by GAT in order to know the agreement between these methods after and before the application of these eyedrops, using the ICC (intraclass correlation coefficient) and the Bland-Altmann method

Simulació de vent en temps real per paisatges

La simulació de la realitat és un fenomen que va sorgir fa uns anys per tal de predir esdeveniments sense haver de malbaratar recursos. El problema inicial de la simulació va ser la necessitat de simplificar la realitat a causa de la manca de capacitat dels ordinadors de l’època. Amb aquest projecte volem ajudar, per exemple, a estudis científics sobre la difusió de la contaminació en grans nuclis a causa de l’efecte del vent, càlculs de trajectòries amb forces externes degudes al vent, o incorporar en el món de la multimèdia efectes realistes de vent. El principal objectiu d’aquest projecte és desenvolupar un sistema que permeti realitzar simulacions realistes de vent per un paisatge 2D, i estudiar com el vent és veu afectat per la geometria de l’escena. Un punt important, és que tot ha de ser en temps real. Per aconseguir-ho, utilitzarem tècniques basades en el mètode de Lattice-Boltzmann, el qual consisteix en una xarxa regular que representa el fluid en posicions discretes, i estudiar com flueix. Escollint els paràmetres correctes de la simulació, es pot demostrar que aquest mètode convergeix a les equacions continues de Navier-Stokes, les qual són les més importants per descriure el comportament macroscòpic d’un fluid. Per accelerar tots els càlculs, utilitzarem la capacitat i la potencia de les targes gràfiques, ajustarem l’algorisme per poder-lo utilitzar en paral•lel, tot tenint en compte les restriccions de les GPUs. També haurem de generar un sistema per poder llegir les escenes 2D sobre les que realitzarem la simulació. Finalment, haurem de “pintar” el vent per tal de poder visualitzar el resultat de la simulació

Extraction and isolation of dictamnine, obacunone and fraxinellone from Dictamnus dasycarpus Turcz. by supercritical fluid extraction and high-speed counter-current chromatography

Supercritical fluid extraction was used to extract active compounds from the Chinese traditional medicinal D. dasycarpus under the pressure of 30 MPa and temperature of 45 ºC. Further separation and purification was established by high-speed counter-current chromatography (HSCCC) with a two-phase solvent system composed of n-hexane-ethyl acetate-methanol-water (1:0.8:1.3:0.9, volume ratio). The separation yielded a total of 47 mg of dictamnine, 24 mg of obacunone and 83 mg of fraxinellone from 1.0 g of the crude extract in one step separation with the purity of 99.2, 98.4 and 99.0%, respectively, as determined by HPLC. The chemical structures of these compounds were identified by ESI-MS, IR, ¹H-NMR and 13C-NMR.

Intraspecific variability of Holostylis reniformis: concentration of lignans, as determined by maceration and supercritical fluid extraction (SFE-CO2), as a function of plant provenance and plant parts

Maceration and supercritical fluid extraction were used to prepare extracts from parts of plants (Holostylis reniformis) collected in two different regions of Brazil. ¹H NMR, HPLC-DAD-ESI/MS, HPLC-DAD, GC-MS, and chemometric techniques were used to analyse lignans in the extracts and showed that yields of SFE-CO2 were less than or equal to those of hexane maceration extracts. These analyses, in conjunction with the concentrations of aliphatic hydrocarbons, fatty acids and their methyl and ethyl derivatives in the extracts, also allowed the chemical composition of parts and provenance of the plant to be differentiated.

Super/subcritical fluid chromatography with packed columns: state of the art and applications

Separations using supercritical fluid chromatography (SFC) with packed columns have been re-discovered and explored in recent years. SFC enables fast and efficient separations and, in some cases, gives better results than high performance liquid chromatography (HPLC). This paper provides an overview of recent advances in SFC separations using packed columns for both achiral and chiral separations. The most important types of stationary phases used in SFC are discussed as well as the most critical parameters involved in the separations and some recent applications.

INTERACTIONS: DESIGN, IMPLEMENTATION AND EVALUATION OF A COMPUTATIONAL TOOL FOR TEACHING INTERMOLECULAR FORCES IN HIGHER EDUCATION

Intermolecular forces are a useful concept that can explain the attraction between particulate matter as well as numerous phenomena in our lives such as viscosity, solubility, drug interactions, and dyeing of fibers. However, studies show that students have difficulty understanding this important concept, which has led us to develop a free educational software in English and Portuguese. The software can be used interactively by teachers and students, thus facilitating better understanding. Professors and students, both graduate and undergraduate, were questioned about the software quality and its intuitiveness of use, facility of navigation, and pedagogical application using a Likert scale. The results led to the conclusion that the developed computer application can be characterized as an auxiliary tool to assist teachers in their lectures and students in their learning process of intermolecular forces.

Numerical modelling of small supersonic axial flow turbines

Supersonic axial turbine stages typically exhibit lower efficiencies than subsonic axial turbine stages. One reason for the lower efficiency is the occurrence of shock waves. With higher pressure ratios the flow inside the turbine becomes relatively easily supersonic if there is only one turbine stage. Supersonic axial turbines can be designed in smaller physical size compared to subsonic axial turbines of same power. This makes them good candidates for turbochargers in large diesel engines, where space can be a limiting factor. Also the production costs are lower for a supersonic axial turbine stage than for two subsonic stages. Since supersonic axial turbines are typically low reaction turbines, they also create lower axial forces to be compensated with bearings compared to high reaction turbines. The effect of changing the stator-rotor axial gap in a small high (rotational) speed supersonic axial flow turbine is studied in design and off-design conditions. Also the effect of using pulsatile mass flow at the supersonic stator inlet is studied. Five axial gaps (axial space between stator and rotor) are modeled using threedimensional computational fluid dynamics at the design and three axial gaps at the off-design conditions. Numerical reliability is studied in three independent studies. An additional measurement is made with the design turbine geometry at intermediate off-design conditions and is used to increase the reliability of the modelling. All numerical modelling is made with the Navier-Stokes solver Finflo employing Chien’s k ¡ ² turbulence model. The modelling of the turbine at the design and off-design conditions shows that the total-to-static efficiency of the turbine decreases when the axial gap is increased in both design and off-design conditions. The efficiency drops almost linearily at the off-design conditions, whereas the efficiency drop accelerates with increasing axial gap at the design conditions. The modelling of the turbine stator with pulsatile inlet flow reveals that the mass flow pulsation amplitude is decreased at the stator throat. The stator efficiency and pressure ratio have sinusoidal shapes as a function of time. A hysteresis-like behaviour is detected for stator efficiency and pressure ratio as a function of inlet mass flow, over one pulse period. This behaviour arises from the pulsatile inlet flow. It is important to have the smallest possible axial gap in the studied turbine type in order to maximize the efficiency. The results for the whole turbine can also be applied to some extent in similar turbines operating for example in space rocket engines. The use of a supersonic stator in a pulsatile inlet flow is shown to be possible.

Simulating Fluid Flow in a Compressed Valve

The objective of the work is to study fluid flow behavior through a pinch valve and to estimate the flow coefficient (KV ) at different opening positions of the valve. The flow inside a compressed valve is more complex than in a straight pipe, and it is one of main topics of interest for engineers in process industry. In the present work, we have numerically simulated compressed valve flow at different opening positions. In order to simulate the flow through pinch valve, several models of the elastomeric valve tube (pinch valve tube) at different opening positions were constructed in 2D-axisymmetric and 3D geometries. The numerical simulations were performed with the CFD packages; ANSYS FLUENT and ANSYS CFX by using parallel computing. The distributions of static pressure, velocity and turbulent kinetic energy have been studied at different opening positions of the valve in both 2D-axisymmetric and 3D experiments. The flow coefficient (KV ) values have been measured at different valve openings and are compared between 2D-axisymmetric and 3D simulation results.

Methods and Models for Accelerating Dynamic Simulation of Fluid Power Circuits

The objective of this dissertation is to improve the dynamic simulation of fluid power circuits. A fluid power circuit is a typical way to implement power transmission in mobile working machines, e.g. cranes, excavators etc. Dynamic simulation is an essential tool in developing controllability and energy-efficient solutions for mobile machines. Efficient dynamic simulation is the basic requirement for the real-time simulation. In the real-time simulation of fluid power circuits there exist numerical problems due to the software and methods used for modelling and integration. A simulation model of a fluid power circuit is typically created using differential and algebraic equations. Efficient numerical methods are required since differential equations must be solved in real time. Unfortunately, simulation software packages offer only a limited selection of numerical solvers. Numerical problems cause noise to the results, which in many cases leads the simulation run to fail. Mathematically the fluid power circuit models are stiff systems of ordinary differential equations. Numerical solution of the stiff systems can be improved by two alternative approaches. The first is to develop numerical solvers suitable for solving stiff systems. The second is to decrease the model stiffness itself by introducing models and algorithms that either decrease the highest eigenvalues or neglect them by introducing steady-state solutions of the stiff parts of the models. The thesis proposes novel methods using the latter approach. The study aims to develop practical methods usable in dynamic simulation of fluid power circuits using explicit fixed-step integration algorithms. In this thesis, twomechanisms whichmake the systemstiff are studied. These are the pressure drop approaching zero in the turbulent orifice model and the volume approaching zero in the equation of pressure build-up. These are the critical areas to which alternative methods for modelling and numerical simulation are proposed. Generally, in hydraulic power transmission systems the orifice flow is clearly in the turbulent area. The flow becomes laminar as the pressure drop over the orifice approaches zero only in rare situations. These are e.g. when a valve is closed, or an actuator is driven against an end stopper, or external force makes actuator to switch its direction during operation. This means that in terms of accuracy, the description of laminar flow is not necessary. But, unfortunately, when a purely turbulent description of the orifice is used, numerical problems occur when the pressure drop comes close to zero since the first derivative of flow with respect to the pressure drop approaches infinity when the pressure drop approaches zero. Furthermore, the second derivative becomes discontinuous, which causes numerical noise and an infinitely small integration step when a variable step integrator is used. A numerically efficient model for the orifice flow is proposed using a cubic spline function to describe the flow in the laminar and transition areas. Parameters for the cubic spline function are selected such that its first derivative is equal to the first derivative of the pure turbulent orifice flow model in the boundary condition. In the dynamic simulation of fluid power circuits, a tradeoff exists between accuracy and calculation speed. This investigation is made for the two-regime flow orifice model. Especially inside of many types of valves, as well as between them, there exist very small volumes. The integration of pressures in small fluid volumes causes numerical problems in fluid power circuit simulation. Particularly in realtime simulation, these numerical problems are a great weakness. The system stiffness approaches infinity as the fluid volume approaches zero. If fixed step explicit algorithms for solving ordinary differential equations (ODE) are used, the system stability would easily be lost when integrating pressures in small volumes. To solve the problem caused by small fluid volumes, a pseudo-dynamic solver is proposed. Instead of integration of the pressure in a small volume, the pressure is solved as a steady-state pressure created in a separate cascade loop by numerical integration. The hydraulic capacitance V/Be of the parts of the circuit whose pressures are solved by the pseudo-dynamic method should be orders of magnitude smaller than that of those partswhose pressures are integrated. The key advantage of this novel method is that the numerical problems caused by the small volumes are completely avoided. Also, the method is freely applicable regardless of the integration routine applied. The superiority of both above-mentioned methods is that they are suited for use together with the semi-empirical modelling method which necessarily does not require any geometrical data of the valves and actuators to be modelled. In this modelling method, most of the needed component information can be taken from the manufacturer’s nominal graphs. This thesis introduces the methods and shows several numerical examples to demonstrate how the proposed methods improve the dynamic simulation of various hydraulic circuits.