Thermogravimetric and mass-spectrometric study of the thermal decomposition of PBCT resins

The thermal decomposition of three commercial samples of carboxy-terminated polybutadiene (PBCT) resins was studied by thermogravimetric analysis (TGA) at heating rates varying from 2° to 100°C/min. Kinetic parameters of the decomposition process at different heating rates were evaluated by means of the Fuoss method.1 The decomposition process and the activation energy values are found to be dependent on heating rate. Mass-spectrometric analysis of the decomposition products shows that the pyrolysis products of PBCT resins are mainly low molecular weight hydrocarbons: ethylene, acetylene, butadiene, propadiene, vinylcyclohexene, etc. The rates of evolution of these hydrocarbon products vary with the carboxy content of the PBCT resin. Based on this, a carbonium ion mechanism has been suggested for the thermal decomposition. The data generated from this work are of importance for a consideration of the mechanism of combustion of composite solid propellants based on PBCT binders.

1-Anilino-8-naphthalene sulfonate (ANS) binding to proteins revisited: Investigation of dye binding to molten globule states by electrospray ionization mass spectrometry

The binding of 1-anilino-8-naphthalene-sulfonic acid to globular proteins at acidic pH has been investigated by electrospray ionization mass spectrometry (ESIMS). Mass spectra of apomyoglobin recorded in the pH range 2−7 establish that maximal ANS binding is observed at pH 4.0. As many as seven distinct species may be observed in the gas phase which correspond to protein molecules containing one to six molecules of bound ANS. At neutral pH only a single molecule of ANS is bound. In the case of cytochrome c, maximal binding is observed at pH 4.0, with five molecules being bound. Binding is suppressed at neutral pH. In both cases ESIMS demonstrates maximal ANS binding at pH values where the proteins have been reported to exist in molten globule states. ANS binding is not observed for lysozyme, which has a tightly folded structure over the entire pH range. Reduction of disulfide bonds in lysozyme leads to the detection of ANS-bound species at neutral pH. Binding is suppressed at low pH due to complete unfolding of the reduced protein. The results suggest that ESIMS may provide a convenient method of probing the stoichiometry and distribution of dye complexes with molten protein globules

Accurate mass-based analysis in human sport doping control : Application of liquid chromatography - time-of-flight mass spectrometry

Human sport doping control analysis is a complex and challenging task for anti-doping laboratories. The List of Prohibited Substances and Methods, updated annually by World Anti-Doping Agency (WADA), consists of hundreds of chemically and pharmacologically different low and high molecular weight compounds. This poses a considerable challenge for laboratories to analyze for them all in a limited amount of time from a limited sample aliquot. The continuous expansion of the Prohibited List obliges laboratories to keep their analytical methods updated and to research new available methodologies. In this thesis, an accurate mass-based analysis employing liquid chromatography - time-of-flight mass spectrometry (LC-TOFMS) was developed and validated to improve the power of doping control analysis. New analytical methods were developed utilizing the high mass accuracy and high information content obtained by TOFMS to generate comprehensive and generic screening procedures. The suitability of LC-TOFMS for comprehensive screening was demonstrated for the first time in the field with mass accuracies better than 1 mDa. Further attention was given to generic sample preparation, an essential part of screening analysis, to rationalize the whole work flow and minimize the need for several separate sample preparation methods. Utilizing both positive and negative ionization allowed the detection of almost 200 prohibited substances. Automatic data processing produced a Microsoft Excel based report highlighting the entries fulfilling the criteria of the reverse data base search (retention time (RT), mass accuracy, isotope match). The quantitative performance of LC-TOFMS was demonstrated with morphine, codeine and their intact glucuronide conjugates. After a straightforward sample preparation the compounds were analyzed directly without the need for hydrolysis, solvent transfer, evaporation or reconstitution. The hydrophilic interaction technique (HILIC) provided good chromatographic separation, which was critical for the morphine glucuronide isomers. A wide linear range (50-5000 ng/ml) with good precision (RSD<10%) and accuracy (±10%) was obtained, showing comparable or better performance to other methods used. In-source collision-induced dissociation (ISCID) allowed confirmation analysis with three diagnostic ions with a median mass accuracy of 1.08 mDa and repeatable ion ratios fulfilling WADA s identification criteria. The suitability of LC-TOFMS for screening of high molecular weight doping agents was demonstrated with plasma volume expanders (PVE), namely dextran and hydroxyethylstarch (HES). Specificity of the assay was improved, since interfering matrix compounds were removed by size exclusion chromatography (SEC). ISCID produced three characteristic ions with an excellent mean mass accuracy of 0.82 mDa at physiological concentration levels. In summary, by combining TOFMS with a proper sample preparation and chromatographic separation, the technique can be utilized extensively in doping control laboratories for comprehensive screening of chemically different low and high molecular weight compounds, for quantification of threshold substances and even for confirmation. LC-TOFMS rationalized the work flow in doping control laboratories by simplifying the screening scheme, expediting reporting and minimizing the analysis costs. Therefore LC-TOFMS can be exploited widely in doping control, and the need for several separate analysis techniques is reduced.

Diastereomeric Drug Glucuronides: Enzymatic Glucuronidation and Analysis by Capillary Electrophoresis and Liquid Chromatography-Mass Spectrometry

Foreign compounds, such as drugs are metabolised in the body in numerous reactions. Metabolic reactions are divided into phase I (functionalisation) and phase II (conjugation) reactions. Uridine diphosphoglucuronosyltransferase enzymes (UGTs) are important catalysts of phase II metabolic system. They catalyse the transfer of glucuronic acid to small lipophilic molecules and convert them to hydrophilic and polar glucuronides that are readily excreted from the body. Liver is the main site of drug metabolism. Many drugs are racemic mixtures of two enantiomers. Glucuronidation of a racemic compound yields a pair of diastereomeric glucuronides. Stereoisomers are interesting substrates in glucuronidation studies since some UGTs display stereoselectivity. Diastereomeric glucuronides of O-desmethyltramadol (M1) and entacapone were selected as model compounds in this work. The investigations of the thesis deal with enzymatic glucuronidation and the development of analytical methods for drug metabolites, particularly diastereomeric glucuronides. The glucuronides were analysed from complex biological matrices, such as urine or from in vitro incubation matrices. Various pretreatment techniques were needed to purify, concentrate and isolate the analytes of interest. Analyses were carried out by liquid chromatography (LC) with ultraviolet (UV) or mass spectrometric (MS) detection or with capillary electromigration techniques. Commercial glucuronide standards were not available for the studies. Enzyme-assisted synthesis with rat liver microsomes was therefore used to produce M1 glucuronides as reference compounds. The glucuronides were isolated by LC/UV and ultra performance liquid chromatography (UPLC)/MS, while tandem mass spectrometry (MS/MS) and nuclear magnetic resonance (NMR) spectroscopy were employed in structural characterisation. The glucuronides were identified as phenolic O-glucuronides of M1. To identify the active UGT enzymes in (±)-M1 glucuronidation recombinant human UGTs and human tissue microsomes were incubated with (±)-M1. The study revealed that several UGTs can catalyse (±)-M1 glucuronidation. Glucuronidation in human liver microsomes like in rat liver microsomes is stereoselective. The results of the studies showed that UGT2B7, most probably, is the main UGT responsible for (±)-M1 glucuronidation in human liver. Large variation in stereoselectivity of UGTs toward (±)-M1 enantiomers was observed. Formation of M1 glucuronides was monitored with a fast and selective UPLC/MS method. Capillary electromigration techniques are known for their high resolution power. A method that relied on capillary electrophoresis (CE) with UV detection was developed for the separation of tramadol and its free and glucuronidated metabolites. The suitability of the method to identify tramadol metabolites in an authentic urine samples was tested. Unaltered tramadol and four of its main metabolites were detected in the electropherogram. A micellar electrokinetic chromatography (MEKC) /UV method was developed for the separation of the glucuronides of entacapone in human urine. The validated method was tested in the analysis of urine samples of patients. The glucuronides of entacapone could be quantified after oral entacapone dosing.

Development of atmospheric pressure ionization ion mobility spectrometry and ion mobility spectrometry mass spectrometry

This study is focused on the development and evaluation of ion mobility instrumentation with various atmospheric pressure ionization techniques and includes the following work. First, a high-resolution drift tube ion mobility spectrometer (IMS), coupled with a commercial triple quadrupole mass spectrometer (MS), was developed. This drift tube IMS is compatible with the front-end of commercial Sciex mass spectrometers (e.g., Sciex API-300, 365, and 3000) and also allows easy (only minor modifications are needed) installation between the original atmospheric pressure ion source and the triple quadrupole mass spectrometer. Performance haracteristics (e.g.,resolving power, detection limit, transmission efficiency of ions) of this IMS-MS instrument were evaluated. Development of the IMS-MS instrument also led to a study where a proposal was made that tetraalkylammonium ions can be used as chemical standards for ESI-IMS. Second, the same drift tube design was also used to build a standalone ion mobility spectrometer equipped with a Faraday plate detector. For this highresolution (resolving power about 100 shown) IMS device, a multi-ion source platform was built, which allows the use of a range of atmospheric pressure ionization methods, such as: corona discharge chemical ionization (CD-APCI), atmospheric pressure photoionization (APPI), and radioactive atmospheric pressure chemical ionization (R-APCI). The multi-ion source platform provides easy switching between ionization methods and both positive and negative ionization modes can be used. Third, a simple desorpion/ionization on silicon (DIOS) ion source set-up for use with the developed IMS and IMS-MS instruments was built and its operation demonstrated. Fourth, a prototype of a commercial aspiration-type ion mobility spectrometer was mounted in front of a commercial triple quadrupole mass spectrometer. The set-up, which is simple, easy to install, and requires no major modifications to the MS, provides the possibility of gathering fundamental information about aspiration mobility spectrometry.

Analysis of heat and mass transfer during bulk hydraircooling of spherical food products

Hydraircooling is a technique used for precooling food products. In this technique chilled water is sprayed over the food products while cold unsaturated air is blown over them. Hydraircooling combines the advantages of both air- and hydrocooling. The present study is concerned with the analysis of bulk hydraircooling as it occurs in a package filled with several layers of spherical food products with chilled water sprayed from the top and cold unsaturated air blown from the bottom. A mathematical model is developed to describe the hydrodynamics and simultaneous heat and mass transfer occurring inside the package. The non-dimensional governing equations are solved using the finite difference numerical methods. The results are presented in the form of time-temperature charts. A correlation is obtained to calculate the process time in terms of the process parameters.

Aktiiviseen kansalaisuuteen kasvattaminen yläkoulun maantieteen opetuksessa

Tutkielmassa tarkasteltiin aktiivista kansalaisuutta perusopetuksen yläkoulun (luokat 7–9) maantieteen opetuksessa. Tutkielman taustana olivat aktiiviseen kansalaisuuteen liittyvät viralliset ja epäviralliset diskurssit: opetussuunnitelman perusteiden aihekokonaisuudet, kouluun kohdistuvat kansalaiskasvatushankkeet sekä nuoriin, kansalaisuuteen ja kansalaisyhteiskuntaan liittyvät keskustelut. Maantieteen opetuksen osalta taustana olivat opetussuunnitelman velvoitteet huomioida aktiivinen kansalaisuus yläkoulun maantieteen opetuksessa sekä (pääasiassa brittiläinen) kirjallisuus, jossa maantieteen ja kansalaiskasvatuksen/aktiivisen kansalaisuuden välillä nähdään yhtäläisyyksiä. Tutkielmassa pyrittiin selvittämään, mitä aktiivinen kansalaisuus on yläkoulun maantieteen opetuksessa ja miten maantieteen opettajat suhtautuvat tehtäviinsä nuorten kansalaisten kasvattajina ja yhteiskunnallisina vaikuttajina. Tutkielmaa varten kerättiin teemahaastatteluaineisto kuudelta yläkoulun maantieteen opettajalta. Haastatteluihin pyrittiin löytämään mahdollisimman aktiivisia maantieteen opettajia. Haastatteluaineiston analyysissa käytettiin sisällönanalyysia, ja aineiston avulla pyrittiin kuvaamaan ilmiötä. Haastateltujen opettajien mukaan yläkoulun maantieteen opetuksessa luonnonmaantieteelliset sisällöt painottuvat enemmän kuin kulttuurimaantieteelliset. Aktiivisen kansalaisuuden kannalta keskeisiä sisältöjä, kuten vaikutusmahdollisuuksia oman ympäristön suunnitteluun ja kehittymiseen sekä kotikunnan ja lähiympäristön tutkimista käsitellään opetuksessa vain vähän, jos ollenkaan. Aktiivinen kansalaisuus on yläkoulun maantieteen opetuksessa eniten tiedon jakamista, ajattelun taitojen ja mielipiteen muodostamisen harjoittelua sekä ympäristövastuullisuuteen kansalaisuuteen kasvattamista. Opetuksessa käytetään myös aktiivisen kansalaisuuden kannalta keskeisiä työtapoja, mutta työtapojen käyttö vaihtelee. Haastatellut opettajat eivät koe opetussuunnitelman aihekokonaisuuksia juurikaan omakseen. Opettajat eivät myöskään määrittele kansalaisvaikuttamiseen kasvattamista koulun tärkeimpien tehtävien joukkoon. Osa opettajista kokee kuitenkin olevansa yhteiskunnallinen vaikuttaja opettajana. Opettajien puheessa koulun kansalaiskasvatuksen tavoite, kunnon kansalainen, ei määrity kovin aktiivisena tai poliittisena. Opettajien puhe sisältää kuitenkin monenlaisia näkemyksiä suhteessa nuoriin kansalaisina ja aktiivisuuteen: toisaalta nuoret eivät ole kiinnostuneita yhteiskunnallisista asioista eikä heiltä vaaditakaan sitä, toisaalta maaperä nuorten kasvattamiseen aktiivisiksi kansalaisiksi on hyvä ja aktiivisuus on pieniä asioita lähiympäristössä sekä yhdessä tekemiseen uskomista. Haastattelujen pohjalta todettiin, että lukuun ottamatta joidenkin opettajien ympäristökasvatuksellista otetta, aktiivinen kansalaisuus ei ole täysin tiedostettu tavoite yläkoulun maantieteen opetuksessa.

Simultaneous heat and mass transfer under unsteady mixed convection along a vertical slender cylinder embedded in a porous medium

Unsteady laminar mixed convection flow (combined free and forced convection flow) along a vertical slender cylinder embedded in a porous medium under the combined buoyancy effect of thermal and species diffusion has been studied. The effect of the permeability of the medium as well as the magnetic field has been included in the analysis. The partial differential equations with three independent variables governing the flow have been solved numerically using a implicit finite difference scheme in combination with the quasilinearization technique. Computations have been carried out for accelerating, decelerating and oscillatory free stream velocity distributions. The effects of the permeability of the medium, buoyancy forces, transverse curvature and magnetic field on skin friction, heat transfer and mass transfer have been studied. It is found that the effect of free stream velocity distribution is more pronounced on the skin friction than on the heat and mass transfer. The permeability and magnetic parameters increase the skin friction, but reduce the heat and mass transfer. The skin friction, heat transfer and mass transfer are enhanced due to the buoyancy forces and curvature parameter. The heat transfer is strongly dependent on the viscous dissipation parameter and the Prandtl number, and the mass transfer on the Schmidt number. Untersucht wurde die instationäre laminare Mischkonvektion längs eines vertikalen, in einem porösen Medium eingebetteten Zylinders unter kombinierten Auftriebseffekten von thermischer und spezieller Diffusion. Der Einfluß der Permeabilität des Mediums sowie des magnetischen Feldes wurden in die Betrachtung einbezogen. Die partiellen Differentialgleichungen mit drei unabhängigen Variablen, welche die Strömung beschreiben, wurde numerisch anhand des Schemas der endlichen Differenzen in Verbindung mit der Technik der Quasilinearisation gelöst. Berechnungen für die beschleunigte, verzögerte und oszillierende Geschwindigkeitsverteilung der freien Strömung sind durchgeführt worden. Untersucht wurden ebenfalls die Effekte der Permeabilität des Mediums, der Auftriebskräfte, der transversalen Krümmung, des magnetischen Feldes auf die Oberflächenreibung sowie die Wärmeund Stoffübertragung. Es wurde festgestellt, daß die Geschwindigkeit mehr Einfluß auf die Oberflächenreibung als auf die Wärmeund Stoffübertragung hat. Die Oberflächenreibung sowie die Wärme- und Stoffübertragung werden durch die Auftriebskräfte und die Krümmungsparameter verbessert. Die Wärmeübertragung ist stark abhängig von den Parametern der viskosen Dissipation und der Prandtl-Zahl; die Stoffübertragung von der Schmidt-Zahl.

Tuning the electronic effective mass in double-doped SrTiO3

We elucidate the relationship between effective mass and carrier concentration in an oxide semiconductor controlled by a double-doping mechanism. In this model oxide system, Sr1-xLaxTiO3-delta, we can tune the effective mass ranging from 6 to 20m(e) as a function of filling (carrier concentration) and the scattering mechanism, which are dependent on the chosen lanthanum-and oxygen-vacancy concentrations. The effective mass values were calculated from the Boltzmann transport equation using the measured transport properties of thin films of Sr1-xLaxTiO3-delta. We show that the effective mass decreases with carrier concentration in this large-band-gap, low-mobility oxide, and this behavior is contrary to the traditional high-mobility, small-effective-mass semiconductors.

Resolution of conflicting views on thermodynamics of glass transition: A unified model

Classical description of thermodynamic properties during glass transition has been questioned by the entropy-loss model. The uncompensated loss of entropy at the glass transition temperature and zero residual entropy is at the heart of the controversy. Both the models are critically reviewed. A unified model is presented which incorporates features of both entropy loss and residual entropy. It implies two different types of contributions to the entropy of the supercooled liquid, one of which vanishes at the transition and the other which contributes to residual entropy. Entropy gain during spontaneous relaxation of glass, and the nature of heat capacity `hysteresis' during cooling and heating through the glass transition range support the proposed model. Experiments are outlined for differentiating between the models.

Mass transfer and shear rate in baffled surface aerator

The scale up or scale down of the process variables in a surface aerator requires information about the shear rate prevailing in the system. In fact, the performance of surface aerator depends upon the shear rate. Shear rate affects the mass transfer operation needed by the surface aerator. Theoretical analysis of shear rate suggests a nonlinear behavior with rotational speed of the impeller, which has been shown in the present work. Present work also shows that in a geometrically similar system of baffled surface aerator, shear rate can be used as a governing parameter for scaling up or down the mass transfer phenomena.

Evolving Philosophies on Autonomous Obstacle/Collision Avoidance of Unmanned Aerial Vehicles

Much of the benefits of deploying unmanned aerial vehicles can be derived from autonomous missions. For such missions, however, sense-and-avoid capability (i.e., the ability to detect potential collisions and avoid them) is a critical requirement. Collision avoidance can be broadly classified into global and local path-planning algorithms, both of which need to be addressed in a successful mission. Whereas global path planning (which is mainly done offline) broadly lays out a path that reaches the goal point, local collision-avoidance algorithms, which are usually fast, reactive, and carried out online, ensure safety of the vehicle from unexpected and unforeseen obstacles/collisions. Even though many techniques for both global and local collision avoidance have been proposed in the recent literature, there is a great interest around the globe to solve this important problem comprehensively and efficiently and such techniques are still evolving. This paper presents a brief overview of a few promising and evolving ideas on collision avoidance for unmanned aerial vehicles, with a preferential bias toward local collision avoidance.