Développement d’une nouvelle méthode d’analyse multi-résidus par LDTD/APCI-MS/MS pour la quantification de pesticides et de produits pharmaceutiques dans les eaux usées

Une nouvelle méthode d'extraction en phase solide (SPE) couplée à une technique d'analyse ultrarapide a été développée pour la détermination simultanée de neuf contaminants émergents (l'atrazine, le déséthylatrazine, le 17(béta)-estradiol, l'éthynylestradiol, la noréthindrone, la caféine, la carbamazépine, le diclofénac et le sulfaméthoxazole) provenant de différentes classes thérapeutiques et présents dans les eaux usées. La pré-concentration et la purification des échantillons a été réalisée avec une cartouche SPE en mode mixte (Strata ABW) ayant à la fois des propriétés échangeuses de cations et d'anions suivie d'une analyse par une désorption thermique par diode laser/ionisation chimique à pression atmosphérique couplée à la spectrométrie de masse en tandem (LDTD-APCI-MS/MS). La LDTD est une nouvelle méthode d'introduction d'échantillon qui réduit le temps total d'analyse à moins de 15 secondes par rapport à plusieurs minutes avec la chromatographie liquide couplée à la spectrométrie de masse en tandem traditionnelle (LC-MS/MS). Plusieurs paramètres SPE ont été évalués dans le but d'optimiser l'efficacité de récupération lors de l'extraction des analytes provenant des eaux usées, tels que la nature de la phase stationnaire, le débit de chargement, le pH d'extraction, le volume et la composition de la solution de lavage et le volume de l'échantillon initial. Cette nouvelle méthode a été appliquée avec succès à de vrais échantillons d'eaux usées provenant d'un réservoir de décantation primaire. Le recouvrement des composés ciblés provenant des eaux usées a été de 78 à 106%, la limite de détection a été de 30 à 122 ng L-1, alors que la limite de quantification a été de 88 à 370 ng L-1. Les courbes d'étalonnage dans les matrices d'eaux usées ont montré une bonne linéarité (R2 > 0,991) pour les analytes cibles ainsi qu’une précision avec un coefficient de variance inférieure à 15%.

Défauts et diffusion dans le silicium amorphe

Nous avons observé une augmentation ‘’transient’’du taux de cristallisation interfacique de l’a-Si lorsqu’on réimplante du Si à proximité de l’interface amorphe/cristal. Après amorphisation et traitement thermique à 650°C pendant 5s de la couche a-Si crée par implantation ionique, une partie a été réimplantée. Les défauts produits par auto-réimplantation à 0.7MeV se trouvent à (302±9) nm de l’interface initiale. Cela nous a permis d’étudier d’avantage la variation initiale de la vitesse SPE (Épitaxie en phase solide). Avec des recuit identiques de 4h à 500°C, nous avons déterminé les positions successives des interfaces et en déduit les taux de cristallisation SPE. La cristallisation débute à l’interface et continue graduellement vers la surface. Après le premier recuit, (252±11) nm s’est recristallisé dans la zone réimplantée soit un avancement SPE de 1.26x10^18at./cm2. Cette valeur est environ 1.50 fois plus importante que celle dans l’état relaxé. Nous suggérons que la présence de défauts à proximité de l’interface a stimulé la vitesse initiale. Avec le nombre de recuit, l’écart entre les vitesses diminue, les deux régions se cristallisent presque à la même vitesse. Les mesures Raman prises avant le SPE et après chaque recuit ont permis de quantifier l’état de relaxation de l’a-Si et le transfert de l’état dé-relaxé à relaxé.

Développement d’une méthode de transfert de protéines présentes dans des sections tissulaires minces sur des cibles fonctionnalisées pour augmenter la spécificité de l’imagerie MS du protéome

L’imagerie par spectrométrie de masse (IMS) est une technique en pleine expansion et utilisée dans beaucoup d’études effectuées sur des systèmes biologiques tels que la corrélation entre l’expression moléculaire et l’état de santé d’un tissu et pour étudier la biologie du développement. Cependant, plus particulièrement lors de l’analyse de protéines, seulement les molécules les plus abondantes et/ou les plus facilement ionisables seront détectées. L’une des approches utilisées pour éviter cette limitation est de transférer les protéines de manière sélective à partir d’une section tissulaire mince vers une surface fonctionnalisée tout en maintenant leur organisation spatiale. Dans ce cas, seulement les protéines possédant une affinité pour la surface seront alors retenues alors que les autres seront éliminées. Donc, la nature chimique de cette surface est critique. Les travaux de recherches présentés dans ce mémoire portent sur le développement d’une méthode de transfert des protéines d’une section tissulaire vers une surface composée de nitrocellulose. Cette méthode utilise un système permettant d’effectuer le transfert sans contact physique direct entre les surfaces. De plus, lors du transfert, une pression physique est appliquée. Dans une première approche, la méthode développée a été appliquée en utilisant une section de rein de souris comme échantillon modèle. Des sections sérielles ont été collectées, soit pour être colorées à l’aide d’hématoxyline et d’éosine (H&E) afin de démontrer la régiospécificité du transfert, soit pour être analysées directement par IMS afin de déterminer si les protéines détectées après transfert sont également détecter dans les sections analysées directement. Les résultats obtenus ont démontré qu’un sous-ensemble de protéines a été transféré tout en conservant leur position spatiale initiale dans les sections. Certains signaux observés pour les protéines transférées sont uniques et/ou sont nettement mieux détectés que lors de l’analyse directe d’une section.

Short Isora Fibre Reinforced Natural Rubber Composites

The present study deals with the short isora fibre reinforced natural rubber composites. In recent years there has been a tremendous advancement in the field of science and technology of short fibre reinforced polymer composites. The low density, high strength, high stiffness to weight ratio, excellent durability and design flexibility are the primary reasons for their use in many diversified fields such as air crafts, automobiles, marine industry etc. Compared to the various natural and synthetic fibres used as reinforcement for elastomer composites isora fibre is superior in many aspects. `Isora' is a natural lignocellulosic fibre which is easily available in South India especially in Kerala. The fibre is separated from the bark of the Helicteres isora plant by retting process. This fibre has excellent mechanical properties and is easily amenable to physical and chemical modifications. The study shows that composites with poor interfacial bonding tend to dissipate more energy than that with to interfacial bonding. The mechanical loss also can be related to interfacial bonding. The effect of chemical treatment of isora fibre on damping was also studied. Both in the low and high temperature region which indicates that this composite posseses low damping and hence good interfacial bonding characteristics. Hence these composites are better candidates for high damping applications. Composites with longitudinally oriented fibres showed high storage modulus than transversely oriented ones due to the effective stress transfer between fibre and matrix.

Surface Properties and Catalytic Activity of Manganese Ferrospinels

In recent years considerable advances have been achieved in the study of the surface structure and mechanism of action of environmentally benign heterogeneous catalysts. The study entitled as surface properties and catalytic activity of manganese ferrospinels. In the present study we have prepared manganese ferrospinels of general formula Mn(1-x)BxFe2O4 via low temperature controlled co-precipation method. The study employed low temperature co-precipitation method for the preparation ofMn(1-x)BxFe2O4 specimens, where B is a metal cation such as Cr,Co, Ni,Cu and Zn. The catalytic activities of the systems were investigated for liquid-phase benzoylation of aromatic compounds and phenol hydroxylation and for vapour-phase reactions such as aniline alkylation, phenol methylation and ODH of ethylbenzene. The different series of manganese ferrites are proved to be excellent catalysts for various industrially important reactions such as Friedel-crafts benzoylation of aromatic compounds, methylation of aniline and phenol, hydroxylation of phenol and oxidative dehydrogenation of ethylbenzene. Due to the tightening of the environmental regulations, production of diphenols from phenol hydroxylation and reduction of phenolic pollutants in waste waters using these catalysts can be a promising approach because it demands only simple techniques and produce little environmental pollution.

The Effect of Glass Additives on the Microwave Dielectric Properties of Ba(Mg 1 /3Ta2/3)03 Ceramics

The effect of glass additives on the densification , phase evolution, microstructure and microwave dielectric properties of Ba(Mg1;3 Ta2i3)03 (BMT) was investigated . Different weight percentages of quenched glass such as B203 , Si02, B203-SiO2, ZnO-B203, 5ZnO-2B2O3, Al203-SiO2, Na20-2B203.10H20, BaO-B203-SiO2, MgO-B203-SiO2, PbO-B203-SiO2 , ZnO-B203-SiO2 and 2MgO-Al203-5SiO2 were added to calcined BMT precursor . The sintering temperature of the glass -added BMT samples were lowered down to 1300 °C compared to solid-state sintering where the temperature was 1650 °C. The formation of high temperature satellite phases such as Ba5Ta4O15 and Ba7Ta6O22 were found to be suppressed by the glass addition . Addition of glass systems such as B203, ZnO-B203, 5ZnO-2B203 and ZnO-B203-SiO2 improved the densification and microwave dielectric properties. Other glasses were found to react with BMT to form low-Q phases which prevented densification . The microwave dielectric properties of undoped BMT with a densification of 93 . 1 % of the theoretical density were Cr = 24 . 8, Tr = 8 ppm/°C and Q„ x f= 80,000 GHz. The BMT doped with 1.0 wt% of B203 has Q„ x f = 124,700GHz, Cr = 24.2, and T f = -1.3 ppm /°C. The unloaded Q factor of 0.2 wt% ZnO-B203-doped BMT was 136,500 GHz while that of 1.0 wt% of 5ZnO-2B203 added ceramic was Q„ x f= 141,800 GHz . The best microwave quality factor was observed for ZnO -B203-SiO2 (ZBS) glass-added ceramics which can act as a perfect liquid-phase medium for the sintering of BMT. The microwave dielectric properties of 0.2wt% ZBS-added BMT dielectric was Q„ x f= 152,800 GHz, F,= 25.5, and Tr = - 1.5 ppm/°C

Unusual autofluorescence characteristic of cultured red-rain cells

The red cells found in the red rain in Kerala, India are now considered as a possible case of extraterrestrial life form. These cells can undergo rapid replication even at an extreme high temperature of 300 deg C. They can also be cultured in diverse unconventional chemical substrates. The molecular composition of these cells is yet to be identified. This paper reports the unusual autofluorescence characteristic of the cultured red rain cells. A spectrofluorimetric study has been performed to investigate this, which shows a systematic shift of the fluorescence emission peak wavelength as the excitation wavelength is increased. Conventional biomolecules are not known to have this property. Details of this investigation and the results are discussed.

Studies on grain refinement and alloying additions on the microstructure and mechanical properties of Mg-8Zn-4Al alloy

MAGNESIUM ALLOYS have strong potential for weight reduction in a wide range of technical applications because of their low density compared to other structural metallic materials. Therefore, an extensive growth of magnesium alloys usage in the automobile sector is expected in the coming years to enhance the fuel efficiency through mass reduction. The drawback associated with the use of commercially cheaper Mg-Al based alloys, such as AZ91, AM60 and AM50 are their inferior creep properties above 100ºC due to the presence of discontinuous Mg17A112 phases at the grain boundaries. Although rare earth-based magnesium alloys show better mechanical properties, it is not economically viable to use these alloys in auto industries. Recently, many new Mg-Al based alloy systems have been developed for high temperature applications, which do not contain the Mg17Al12 phase. It has been proved that the addition of a high percentage of zinc (which depends upon the percentage of Al) to binary Mg-Al alloys also ensures the complete removal of the Mg17Al12 phase and hence exhibits superior high temperature properties.ZA84 alloy is one such system, which has 8%Zn in it (Mg-8Zn-4Al-0.2Mn, all are in wt %) and shows superior creep resistance compared to AZ and AM series alloys. These alloys are mostly used in die casting industries. However, there are certain large and heavy components, made up of this alloy by sand castings that show lower mechanical properties because of their coarse microstructure. Moreover, further improvement in their high temperature behaviour through microstructural modification is also an essential task to make this alloy suitable for the replacement of high strength aluminium alloys used in automobile industry. Grain refinement is an effective way to improve the tensile behaviour of engineering alloys. In fact, grain refinement of Mg-Al based alloys is well documented in literature. However, there is no grain refiner commercially available in the market for Mg-Al alloys. It is also reported in the literature that the microstructure of AZ91 alloy is modified through the minor elemental additions such as Sb, Si, Sr, Ca, etc., which enhance its high temperature properties because of the formation of new stable intermetallics. The same strategy can be used with the ZA84 alloy system to improve its high temperature properties further without sacrificing the other properties. The primary objective of the present research work, “Studies on grain refinement and alloying additions on the microstructure and mechanical properties of Mg-8Zn-4Al alloy” is twofold: 1. To investigate the role of individual and combined additions of Sb and Ca on the microstructure and mechanical properties of ZA84 alloy. 2. To synthesis a novel Mg-1wt%Al4C3 master alloy for grain refinement of ZA84 alloy and investigate its effects on mechanical properties.

Effect of deuteration on the electrical conductivity, dielectric constant and phase transitions in LiNH4SO4

Measurements of dc conductivity and dielectric constant show that deuteration causes an upward shift of the high temperature phase transition point from 186.5 to 191°C and a downward shift of the low temperature transition point from 10 to -1.5°C in LiNH4SO4. Mechanisms of phase transitions and of electrical transport in the crystal are discussed.

EPDM/CIIR Blends: Compatibility, Morphology and Physical Properties

A detailed study of the blends of ethylene-propylene-diene rubber (EPDM) and chlorobutyl rubber (CIIR) is proposed in this study. These blends may find application in the manufacture of curing diaphragms/curing envelopes for tire curing applications. EPDM possesses better physical properties such as high heat resistance, ozone resistance, cold and moisture resistance, high resistance to permanent defonnation, very good resistance to flex cracking and impact. Because of the low gas and moisture penneability, good weathering resistance and high thermal stability of CIIR, blends of EPDM with CIlR may be attractive, if sufficient mechanical strength can be developed. Although a lot of work has been done on elastomer blends, studies on the blends of EPDM and CIIR rubbers are meagre. Hence in this investigation it is proposed to make a systematic study on the characteristics of EPDM and CIIR rubber blends.The mechanical and physical properties of an elastomer blend depend mainly on the blend compatibility. So in the first part of the study, it is proposed to develop compatible blends of EPDM with CIIR. Various commercial grades of ethylenepropylene- diene rubber are proposed to be blended with a specific grade of chlorobutyl rubber at varying proportions. The extent of compatibility in these blends is proposed to be evaluated based on their mechanical properties such as tensile strength, tear strength and ageing resistance. In addition to the physical property measurements, blend compatibility is also proposed to be studied based on the glass transition behavlour of the blends in relation to the Tg's of the individual components using Differential Scanning Calorimetry (DSC) and Dynamic Mechanical Analysis (DMA). The phase morphology of the blends is also proposed to be investigated by Scanning Electron Microscopy (SEM) studies of the tensile fracture surfaces. In the case of incompatible blends, the effect of addition of chlorosulfonated polyethylene as a compatibiliser is also proposed to be investigated.In the second part of the study, the effect of sulphur curing and resin curing on the curing behaviour and the vulcanizate properties of EPDM/CIIR blends are planned to be evaluated. Since the properties of rubber vulcanizates are determined by their network structures, it is proposed to determine the network structure of the vulcanizates by chemical probes so as to correlate it with the mechanical properties.In the third part of the work, the effect of partial precuring of one of the components prior to blending as a possible means of improving the properties of the blend is proposed to be investigated. This procedure may also help to bring down the viscosity mismatch between the constituent e1astomers and provide covulcanization of the blend.The rheological characteristics and processability of the blends are proposed to be investigated in the last part of the study. To explore their possible applications, the air permeability of the blend samples at varying temperatures is proposed to be measured. The thermal diffusivity behaviour of EPDM/CIlR blends is also proposed to be investigated using novel laser technique. The thermal diffusivity of the blends along with the thermal degradation resistance may help to determine whether the blends are suitable for high temperature applications such as in the manufacturing of curing envelope.

Novel adhesive systems based on neoprene-phenolic blends

The aim of the investigation is to develop new high performance adhesive systems based on neoprene-phenolic blends. Initially the effect of addition of all possible ingredients like fillers, adhesion promoters, curing agents and their optimum compositions to neoprene solution is investigated. The phenolic resin used is a copolymer of phenol-cardanolformaldehyde prepared in the laboratory. The optimum ratio between phenol and cardanol that gives the maximum bond strength in metal-metal, rubber-rubber and rubber-metal specimens has been identified. Further the ratio between total phenols and formaldehyde is also optimised. The above adhesive system is further modified by the addition of epoxidized phenolic novolacs. For this purpose, phenolic novolac resins are prepared in different stoichiometric ratios and are subsequently epoxidized. The effectiveness of the adhesive for bonding different metal and rubber substrates is another part of the study. To study the ageing behaviour, different bonded specimens are exposed to high temperature, hot water and salt water and adhesive properties have been evaluated. The synthesized resins have been characterized by FTIR , HNMR spectroscopy. The molecular weights of the resins have been obtained by GPC. Thermogravimetric analysis and differential scanning calorimetry are used to study the thermal properties. The fractured surface analysis is studied by scanning electron microscopy. The study has brought to light the influence of phenol/ formaldehyde stoichiometric ratio, addition of cardanol (a renewable resource), adhesion promoters and suitability of the adhesive for different substrates and the age resistance of adhesive joints among other things.

Acoustic radiation and scattering from cylindrical bodies and analysis of transducer arrays

New mathematical methods to analytically investigate linear acoustic radiation and scattering from cylindrical bodies and transducer arrays are presented. Three problems of interest involving cylinders in an infinite fluid are studied. In all the three problems, the Helmholtz equation is used to model propagation through the fluid and the beam patterns of arrays of transducers are studied. In the first problem, a method is presented to determine the omni-directional and directional far-field pressures radiated by a cylindrical transducer array in an infinite rigid cylindrical baffle. The solution to the Helmholtz equation and the displacement continuity condition at the interface between the array and the surrounding water are used to determine the pressure. The displacement of the surface of each transducer is in the direction of the normal to the array and is assumed to be uniform. Expressions are derived for the pressure radiated by a sector of the array vibrating in-phase, the entire array vibrating in-phase, and a sector of the array phase-shaded to simulate radiation from a rectangular piston. It is shown that the uniform displacement required for generating a source level of 220 dB ref. μPa @ 1m that is omni directional in the azimuthal plane is in the order of 1 micron for typical arrays. Numerical results are presented to show that there is only a small difference between the on-axis pressures radiated by phased cylindrical arrays and planar arrays. The problem is of interest because cylindrical arrays of projectors are often used to search for underwater objects. In the second problem, the errors, when using data-independent, classical, energy and split beam correlation methods, in finding the direction of arrival (DOA) of a plane acoustic wave, caused by the presence of a solid circular elastic cylindrical stiffener near a linear array of hydrophones, are investigated. Scattering from the effectively infinite cylinder is modeled using the exact axisymmetric equations of motion and the total pressures at the hydrophone locations are computed. The effect of the radius of the cylinder, a, the distance between the cylinder and the array, b, the number of hydrophones in the array, 2H, and the angle of incidence of the wave, α, on the error in finding the DOA are illustrated using numerical results. For an array that is about 30 times the wavelength and for small angles of incidence (α<10), the error in finding the DOA using the energy method is less than that using the split beam correlation method with beam steered to α; and in some cases, the error increases when b increases; and the errors in finding the DOA using the energy method and the split beam correlation method with beam steered to α vary approximately as a7 / 4 . The problem is of interest because elastic stiffeners – in nearly acoustically transparent sonar domes that are used to protect arrays of transducers – scatter waves that are incident on it and cause an error in the estimated direction of arrival of the wave. In the third problem, a high-frequency ray-acoustics method is presented and used to determine the interior pressure field when a plane wave is normally incident on a fluid cylinder embedded in another infinite fluid. The pressure field is determined by using geometrical and physical acoustics. The interior pressure is expressed as the sum of the pressures due to all rays that pass through a point. Numerical results are presented for ka = 20 to 100 where k is the acoustic wavenumber of the exterior fluid and a is the radius of the cylinder. The results are in good agreement with those obtained using field theory. The directional responses, to the plane wave, of sectors of a circular array of uniformly distributed hydrophones in the embedded cylinder are then computed. The sectors are used to simulate linear arrays with uniformly distributed normals by using delays. The directional responses are compared with the output from an array in an infinite homogenous fluid. These outputs are of interest as they are used to determine the direction of arrival of the plane wave. Numerical results are presented for a circular array with 32 hydrophones and 12 hydrophones in each sector. The problem is of interest because arrays of hydrophones are housed inside sonar domes and acoustic plane waves from distant sources are scattered by the dome filled with fresh water and cause deterioration in the performance of the array.

Polypropylene/metal oxide nanocomposites: fiber spinning and evaluation”

PP has been getting much attention over the years because it is a very durable polymer commonly used in aggressive environments including automotive battery casings, fuel containers etc. They are used to make bottles, fibers for clothing, components in cars etc. However, it has some shortcomings such as low dimensional and thermal stability. Materials such as metal oxides with sizes of the order 1–50 nm have received a great deal of attention because of their versatile applications in polymer/ inorganic nanocomposites, optoelectronic devices, biomedical materials, and other areas. They are stable under harsh process conditions and also regarded as safe materials to human beings and animals. In the present investigation, PP is modified by incorporating metal oxide nanoparticles such as ZnO and TiO2 by simple melt mixing method. Melt spinning method was used to prepare PP/metal oxide nanocomposite fibers. Various studies have been carried out on these composites and fibers. In the first part of the study, ZnO nanoparticles were prepared from ZnCl2 and NaOH in presence of chitosan, PVA, ethanol and starch. This is a simple and inexpensive method compared to other methods. Change in morphology and particle size of ZnO were studied. Least particle size was obtained in chitosan medium. The particles were characterized by using XRD, SEM, TEM, TGA and EDAX. Antibacterial properties of ZnO prepared in chitosan medium (NZO) and commercial zinc oxide (CZO) were evaluated using a gram positive and a gram negative bacteria

Photoacoustic investigation of the optical and thermal properties of selected amorphous chalcogenide semiconductors

This thesis work has mainly concentrated on the investigation of the ,optical and thermal properties of binary semiconducting chalcogenide glasses belonging to the AivB¥5x and AZBXEX families. The technique used for these studies is a relatively new one namely, the photoacoustic (PA) technique. This technique is based on the detection of acoustic signal produced in an enclosed volume when the sample is irradiated by an intensity modulated radiation. The signal produced depends upon the optical properties of the sample, and the thermal properties of the sample, backing material and the surrounding gas. For the present studies an efficient signal beam gas-microphone PA spectrometer, consisting of a high power Xenon lamp, monochromator, light beam chopper, PA cell with microphone and lock-in amplifier, has been set up. Two PA cells have been fabricated: one for room temperature measurements and another for measurements at high temperatures. With the high temperature PA cell measurements can be taken upto 250°C. Provisions are incorporated. in both the cells to change the volume and to use different backing materials for the sample. The cells have been calibrated by measuring the frequency response of the cells using carbon black as the sample

Optical and thermal characterization of dye intercalated montmorillonites and rare earth doped materials

The advent of high optical quality transparent nano—structured glasses, the so-called transparent glass ceramics or vitroceramics disclosed the possibility of producing nano-sized photonic devices based on rare-earth doped up—converters. Transparent glass ceramics have been investigated as hosts for lanthanide ions envisioning the production of materials that are easy to shape and with high performance for photonic applications. Rare earth doped glasses have been extensively studied due to their potential applications in optical devices such as solid state lasers and optical fibers. Various photothermal and optical techniques have been successfully applied for the thermal and optical characterization of these rare earth doped materials. In the present thesis, the effective thermal parameters like thermal diffusivity and thermal effusivity of complex materials for various applications have been investigated using photothermal methods along with their optical characterization utilising the common optical absorption as well as fluorescence spectroscopic techniques. These sensitive optical procedures are also essential for exploiting these materials for further photonic applications.